TWI782914B - Releasing film - Google Patents

Releasing film Download PDF

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TWI782914B
TWI782914B TW106116563A TW106116563A TWI782914B TW I782914 B TWI782914 B TW I782914B TW 106116563 A TW106116563 A TW 106116563A TW 106116563 A TW106116563 A TW 106116563A TW I782914 B TWI782914 B TW I782914B
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adhesive
mass
adhesive layer
electromagnetic wave
polymer
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TW106116563A
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Chinese (zh)
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TW201808629A (en
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石島英明
柳田裕貴
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日商昭和電工材料股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00Adhesives based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56Encapsulations, e.g. encapsulation layers, coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/552Protection against radiation, e.g. light or electromagnetic waves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212Electromagnetic interference shielding
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

A releasing film, comprising: a support that comprises a substrate and an adhesive layer positioned on the substrate; and an electromagnetic wave-shielding sheet positioned on the adhesive layer of the support, the releasing film having a peel force between the adhesive layer and the electromagnetic wave-shielding sheet from 0.10 N/50 mm to 2.00 N/50 mm.

Description

脫模膜Release film

本發明是有關於一種脫模膜。The present invention relates to a release film.

近年來,隨著電子設備的小型化發展,要求半導體元件表面的高密度搭載技術的進一步提高。因此,近年來採用多段地積層多個半導體元件的所謂的堆疊封裝型的半導體裝置。於此種堆疊封裝型的半導體裝置中,將半導體元件以集積的狀態配置,因此可產生由外在雜訊所引起的問題(電磁波阻礙)。此種雜訊的問題越隨著電子設備的數位化、高速化及高頻化發展而越顯著。因此,為了抑制由雜訊所帶來的影響,提出有將用以遮蔽電磁波的電磁波遮蔽片形成於對半導體元件進行密封的密封材上的技術(例如,參照專利文獻1)。In recent years, along with progress in the miniaturization of electronic equipment, further improvement in high-density mounting technology on the surface of semiconductor elements has been demanded. Therefore, in recent years, a so-called package-on-package type semiconductor device in which a plurality of semiconductor elements is stacked in multiple stages has been adopted. In such a package-on-package type semiconductor device, semiconductor elements are arranged in a stacked state, so problems (electromagnetic wave obstruction) caused by external noise may arise. This kind of noise problem becomes more and more obvious with the development of digitization, high speed and high frequency of electronic equipment. Therefore, in order to suppress the influence of noise, there has been proposed a technique in which an electromagnetic wave shielding sheet for shielding electromagnetic waves is formed on a sealing material that seals a semiconductor element (for example, refer to Patent Document 1).

作為電磁波遮蔽片的形成方法,例如已知有專利文獻2中記載的半導體裝置的製造方法。於該製造方法中,於藉由使用上模具及下模具的轉移成型而利用密封材對半導體元件進行密封的步驟中,將用以形成電磁波遮蔽片的材料塗佈於配置於上模具的脫模膜(release film)(載體膜),將該材料轉印至密封材上並進行硬化而形成電磁波遮蔽片。 [現有技術文獻] [專利文獻]As a method of forming an electromagnetic wave shielding sheet, for example, a method of manufacturing a semiconductor device described in Patent Document 2 is known. In this manufacturing method, in the step of sealing the semiconductor element with the sealing material by transfer molding using the upper mold and the lower mold, the material for forming the electromagnetic wave shielding sheet is applied to the release mold placed on the upper mold Release film (carrier film), this material is transferred onto the sealing material and cured to form an electromagnetic wave shielding sheet. [Prior Art Documents] [Patent Documents]

[專利文獻1]日本專利第4133637號公報 [專利文獻2]日本專利特開2007-287937號公報[Patent Document 1] Japanese Patent No. 4133637 [Patent Document 2] Japanese Patent Laid-Open No. 2007-287937

然而,於專利文獻2中記載的方法中,每當利用密封材對半導體裝置進行密封的步驟時,需要每次將用以形成電磁波遮蔽片的材料塗佈於載體膜上的作業,因此就生產效率的觀點而言有改善的餘地。However, in the method described in Patent Document 2, every time the semiconductor device is sealed with a sealing material, it is necessary to apply the material for forming the electromagnetic wave shielding sheet on the carrier film every time, so production From an efficiency point of view, there is room for improvement.

本發明為用以解決所述課題而成者,其目的在於提供一種能夠實現具有電磁波遮蔽片的半導體裝置的生產效率的提高的脫模膜。This invention is made to solve the said subject, and it aims at providing the release film which can aim at the improvement of the production efficiency of the semiconductor device which has an electromagnetic wave shielding sheet.

於用以解決所述課題的手段中包含以下的實施態樣。 <1>一種脫模膜,其包含:支撐體,含有基材及配置於所述基材上的黏著層;以及電磁波遮蔽片,配置於所述支撐體的所述黏著層上,且所述黏著層與所述電磁波遮蔽片之間的剝離力為0.10 N/50 mm~2.00 N/50 mm。 <2>如<1>所述的脫模膜,其中所述電磁波遮蔽片的厚度為0.01 μm~50 μm。 <3>如<1>或<2>所述的脫模膜,其中所述黏著層的厚度為1 μm~20 μm。Means for solving the above-mentioned problems include the following embodiments. <1> A release film comprising: a support body including a base material and an adhesive layer arranged on the base material; and an electromagnetic wave shielding sheet arranged on the adhesive layer of the support body, and the The peeling force between the adhesive layer and the electromagnetic wave shielding sheet is 0.10 N/50 mm to 2.00 N/50 mm. <2> The release film according to <1>, wherein the electromagnetic wave shielding sheet has a thickness of 0.01 μm to 50 μm. <3> The release film according to <1> or <2>, wherein the adhesive layer has a thickness of 1 μm to 20 μm.

<4>如<1>至<3>中任一項所述的脫模膜,其中所述黏著層包含選自由矽酮系黏著劑及丙烯酸系黏著劑所組成的群組中的至少一種。 <4> The release film according to any one of <1> to <3>, wherein the adhesive layer contains at least one selected from the group consisting of silicone adhesives and acrylic adhesives.

<5>如<1>至<4>中任一項所述的脫模膜,其用於半導體裝置的製造,半導體裝置的製造包括將所述電磁波遮蔽片轉印至對半導體元件進行密封的密封材的步驟。 <5> The release film according to any one of <1> to <4>, which is used in the manufacture of a semiconductor device, the manufacture of the semiconductor device including transferring the electromagnetic wave shielding sheet to a semiconductor element for sealing. Steps for sealant.

根據本發明,可提供一種能夠實現具有電磁波遮蔽片的半導體裝置的生產效率的提高的脫模膜。 According to the present invention, it is possible to provide a release film capable of improving the production efficiency of a semiconductor device having an electromagnetic wave shielding sheet.

以下,對用以實施本發明的形態進行詳細說明。但是,本發明並不限定於以下的實施形態。於以下的實施形態中,其構成要素(亦包含要素步驟(step)等)除特別明示的情況以外,並非為必需。數值及其範圍亦相同,並不限制本發明。 Hereinafter, the form for carrying out this invention is demonstrated in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps (steps) and the like) are not essential unless otherwise specified. Numerical values and their ranges are also the same and do not limit the present invention.

本說明書中「步驟」這一用語除與其他步驟獨立的步驟以外,即便於與其他步驟無法明確地加以區分的情況下,只要達成該步驟的目的,亦包括該步驟。 本說明書中使用「~」所表示的數值範圍包含「~」的前後所記載的數值分別作為最小值及最大值。 本說明書中階段性地所記載的數值範圍中,可將一個數值範圍中所記載的上限值或下限值替換為其他階段的記載的數值範圍的上限值或下限值。另外,本說明書中所記載的數值範圍中,可將所述數值範圍的上限值或下限值替換為實施例中所示的值。 本說明書中關於組成物中的各成分的含有率或含量,於在組成物中存在多種相當於各成分的物質的情況下,只要無特別說明,則是指存在於組成物中的該多種物質的合計含有率或含量。 本說明書中關於組成物中的各成分的粒子徑,於在組成物中存在多種相當於各成分的粒子的情況下,只要無特別說明,則是指存在於組成物中的該多種粒子的混合物的值。 本說明書中「層」或「膜」這一用語中,於對該層或膜所存在的區域進行觀察時,除形成於該區域的整體的情況以外,亦包含僅形成於該區域的一部分的情況。 本說明書中「積層」這一用語表示將層累積,可結合有兩個以上的層,亦能夠使兩個以上的層裝卸。 本說明書中「(甲基)丙烯醯基」是指丙烯醯基以及甲基丙烯醯基的至少一者,「(甲基)丙烯酸」是指丙烯酸以及甲基丙烯酸的至少一者,「(甲基)丙烯酸酯」是指丙烯酸酯以及甲基丙烯酸酯的至少一者。The term "step" in this specification includes a step that is independent from other steps, and even when it cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved. The numerical range represented by "-" in this specification includes the numerical value described before and after "-" as a minimum value and a maximum value, respectively. In the numerical ranges described step by step in this specification, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical range described in other stages. In addition, in the numerical range described in this specification, the upper limit or the lower limit of the said numerical range can be replaced with the value shown in an Example. In this specification, the content or content of each component in the composition refers to the plurality of substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. The total content rate or content. In this specification, the particle size of each component in the composition refers to a mixture of the plurality of particles present in the composition, unless otherwise specified, when there are multiple types of particles corresponding to each component in the composition. value. The term "layer" or "film" in this specification, when looking at the area where the layer or film exists, includes not only the case where it is formed in the entire area, but also the case where it is formed in only a part of the area. Condition. The term "lamination" in this specification means that layers are accumulated, and two or more layers may be combined, and two or more layers may be attached and detached. In this specification, "(meth)acryl" means at least one of acryl and methacryl, "(meth)acryl" means at least one of acryl and methacryl, and "(meth)acryl" means at least one of acryl and methacryl. "Base) acrylate" means at least one of acrylate and methacrylate.

本實施形態的脫模膜包含:支撐體,含有基材及配置於所述基材上的黏著層;以及電磁波遮蔽片,配置於所述支撐體的所述黏著層上,且所述黏著層與所述電磁波遮蔽片之間的剝離力為0.10 N/50 mm~2.00 N/50 mm。The release film of this embodiment includes: a support body including a substrate and an adhesive layer arranged on the substrate; and an electromagnetic wave shielding sheet arranged on the adhesive layer of the support body, and the adhesive layer The peeling force with the electromagnetic wave shielding sheet is 0.10 N/50 mm to 2.00 N/50 mm.

本實施形態的脫模膜藉由具有所述構成,即便於密封步驟前預先將電磁波遮蔽片配置於支撐體上,亦可自支撐體良好地剝離電磁波遮蔽片。因此,每當密封步驟時無需將電磁波遮蔽片配置於脫模膜上,或者亦無需於密封後以其他步驟形成電磁波遮蔽層,因此就生產效率的觀點而言有利。因而,本實施形態的脫模膜可較佳地用於具有電磁波遮蔽片的半導體裝置的製造方法(更具體而言,包括將所述電磁波遮蔽片轉印至對半導體元件進行密封的密封材的步驟的半導體裝置的製造方法)中。Since the release film according to the present embodiment has the above structure, even if the electromagnetic wave shielding sheet is previously arranged on the support before the sealing step, the electromagnetic wave shielding sheet can be peeled off favorably from the support. Therefore, it is not necessary to arrange the electromagnetic wave shielding sheet on the release film every sealing step, or to form an electromagnetic wave shielding layer in another step after sealing, which is advantageous from the viewpoint of production efficiency. Therefore, the release film of this embodiment can be preferably used in a method of manufacturing a semiconductor device having an electromagnetic wave shielding sheet (more specifically, a process including transferring the electromagnetic wave shielding sheet to a sealing material for sealing a semiconductor element. Step semiconductor device manufacturing method).

本說明書中,「黏著層與電磁波遮蔽片之間的剝離力」為於170℃的環境下以剝離角度180°及剝離速度0.3 m/min的條件所測定的值(N/50 mm)。剝離力例如可使用騰喜龍(Tensilon)萬能材料試驗機(A&D股份有限公司製造)進行測定。In this specification, the "peeling force between the adhesive layer and the electromagnetic wave shielding sheet" is a value (N/50 mm) measured under the conditions of a peeling angle of 180° and a peeling speed of 0.3 m/min in an environment of 170°C. The peel force can be measured using, for example, a Tensilon universal testing machine (manufactured by A&D Co., Ltd.).

若黏著層與電磁波遮蔽片之間的剝離力為0.10 N/50 mm以上,則有可抑制高溫時的電磁波遮蔽片的剝落的傾向。若黏著層與電磁波遮蔽片之間的剝離力為2.00 N/50 mm以下,則有可充分地獲得電磁波遮蔽片的自黏著層的轉印性的傾向。黏著層與電磁波遮蔽片之間的剝離力較佳為0.20 N/50 mm以上,且較佳為1.60 N/50 mm以下。When the peeling force between the adhesive layer and the electromagnetic wave shielding sheet is 0.10 N/50 mm or more, it tends to suppress the peeling of the electromagnetic wave shielding sheet at high temperature. There exists a tendency for the transferability of the self-adhesive layer of an electromagnetic wave shielding sheet to be fully acquired as the peeling force between an adhesive layer and an electromagnetic wave shielding sheet is 2.00 N/50 mm or less. The peeling force between the adhesive layer and the electromagnetic wave shielding sheet is preferably not less than 0.20 N/50 mm and is preferably not more than 1.60 N/50 mm.

以下,參照圖式對本實施形態的脫模膜進行說明,但本發明並不限定於此。另外,各圖中的構件的大小為概念上的大小,構件間的大小的相對性關係並不限定於此。Hereinafter, although the release film of this embodiment is demonstrated referring drawings, this invention is not limited to this. In addition, the size of the components in each figure is a conceptual size, and the relative relationship of the size between components is not limited to this.

圖1為表示本實施形態的脫模膜的結構的一例的概略剖面圖。脫模膜10包含:支撐體20,含有基材50及配置於基材50上的黏著層40;以及電磁波遮蔽片30,配置於支撐體20的黏著層40上。關於支撐體20,可將黏著層配置於基材50的整個面上,亦可僅配置於一部分上,其形狀並無特別限制。FIG. 1 is a schematic cross-sectional view showing an example of the structure of a release film according to this embodiment. The release film 10 includes: a support body 20 including a base material 50 and an adhesive layer 40 disposed on the base material 50 ; and an electromagnetic wave shielding sheet 30 disposed on the adhesive layer 40 of the support body 20 . Regarding the support body 20, the adhesive layer may be disposed on the entire surface of the substrate 50, or may be disposed on only a part thereof, and its shape is not particularly limited.

於脫模膜10中,只要電磁波遮蔽片30所配置的位置為黏著層40上,則並無特別限制。例如,如圖2的概略平面圖所示般,可將電磁波遮蔽片30僅配置於支撐體20的一部分上,亦可將電磁波遮蔽片30配置於支撐體20的整個面上。電磁波遮蔽片30的形狀並無特別限制,亦可為四邊形、圓形等所期望的形狀。可將電磁波遮蔽片30於多個區域內空開間隔而配置,該情況下的區域間的間隔亦無特別限制。In the release film 10 , as long as the position where the electromagnetic wave shielding sheet 30 is disposed is on the adhesive layer 40 , there is no particular limitation. For example, as shown in the schematic plan view of FIG. 2 , the electromagnetic wave shielding sheet 30 may be disposed on only a part of the support body 20 , or the electromagnetic wave shielding sheet 30 may be disposed on the entire surface of the support body 20 . The shape of the electromagnetic wave shielding sheet 30 is not particularly limited, and may be a desired shape such as a quadrangle or a circle. The electromagnetic wave shielding sheet 30 may be arranged at intervals in a plurality of regions, and the interval between regions in this case is not particularly limited.

將電磁波遮蔽片30配置於黏著層40上的方法並無特別限制。例如可列舉:濺鍍法、蒸鍍法、離子鍍敷法、層壓法等。就相對於黏著層40的密接性的觀點而言,較佳為蒸鍍法、離子鍍敷法或層壓法。電磁波遮蔽片30的材質並無特別限制。例如可列舉金屬。就價格及加工性的觀點而言,較佳為包含選自由銅及鋁所組成的群組中的至少一種金屬元素。The method of disposing the electromagnetic wave shielding sheet 30 on the adhesive layer 40 is not particularly limited. For example, a sputtering method, a vapor deposition method, an ion plating method, a lamination method, etc. are mentioned. From the viewpoint of adhesiveness to the adhesive layer 40 , vapor deposition, ion plating, or lamination are preferable. The material of the electromagnetic wave shielding sheet 30 is not particularly limited. For example, a metal is mentioned. From the viewpoint of price and workability, it is preferable to contain at least one metal element selected from the group consisting of copper and aluminum.

基材50的厚度較佳為20 μm~200 μm,更佳為25 μm~100μm,進而佳為25μm~50μm。若基材50的厚度為20μm以上,則可獲得充分的強度,有可抑制引線框架的翹曲等問題發生的傾向,若為200μm以下,則有對半導體製造裝置的適合性優異的傾向。 The thickness of the substrate 50 is preferably from 20 μm to 200 μm, more preferably from 25 μm to 100 μm, and still more preferably from 25 μm to 50 μm. When the thickness of the base material 50 is 20 μm or more, sufficient strength is obtained, and the occurrence of problems such as warpage of the lead frame tends to be suppressed, and when the thickness is 200 μm or less, the suitability for semiconductor manufacturing equipment tends to be excellent.

黏著層40的厚度較佳為1μm~20μm,更佳為2μm~12μm。若黏著層40的厚度為1μm以上,則有可良好地進行電磁波遮蔽片30的自黏著層40向黏附體的轉印的傾向,若為20μm以下,則有電磁波遮蔽片30於密封步驟中難以自黏著層40剝離的傾向。 The thickness of the adhesive layer 40 is preferably 1 μm˜20 μm, more preferably 2 μm˜12 μm. If the thickness of the adhesive layer 40 is 1 μm or more, there is a tendency that the transfer of the electromagnetic wave shielding sheet 30 from the adhesive layer 40 to the adherend can be performed well, and if it is 20 μm or less, the electromagnetic wave shielding sheet 30 may be difficult to seal in the sealing step. Tendency to peel from the adhesive layer 40 .

電磁波遮蔽片30的厚度較佳為0.01μm~50μm,更佳為0.05μm~12μm。若電磁波遮蔽片30的厚度為0.01μm以上,則有可獲得充分的電磁波遮蔽性的傾向,若為50μm以下,則有加工性優異的傾向。 The thickness of the electromagnetic shielding sheet 30 is preferably from 0.01 μm to 50 μm, more preferably from 0.05 μm to 12 μm. When the thickness of the electromagnetic wave shielding sheet 30 is 0.01 μm or more, sufficient electromagnetic wave shielding property tends to be obtained, and when it is 50 μm or less, the processability tends to be excellent.

本說明書中,將基材50、黏著層40及電磁波遮蔽片30的厚度設為於5點進行測定而獲得的值的數量平均值。厚度的測定方法並無特別限制,可利用公知的方法進行。 In this specification, the thickness of the base material 50, the adhesive layer 40, and the electromagnetic wave shielding sheet 30 is made into the number average of the values measured at 5 points. The method of measuring the thickness is not particularly limited, and a known method can be used.

脫模膜10視需要亦可具有基材50、黏著層40及電磁波遮蔽片30以外的構件。例如,亦可具有用以保護脫模膜10的表面的保護膜。 The release film 10 may have members other than the base material 50, the adhesive layer 40, and the electromagnetic wave shielding sheet 30 as needed. For example, you may have the protective film for protecting the surface of the release film 10.

<黏著層> <adhesive layer>

黏著層只要與電磁波遮蔽片之間的剝離力成為所述範圍內,則並無特別限制。例如可列舉包含矽酮系黏著劑、丙烯酸系黏著劑、橡膠系黏著劑、胺基甲酸酯系黏著劑等黏著劑的層。黏著層中所含的黏著劑可為單獨一種,亦可為兩種以上。 本發明中,黏著層中所含的黏著劑可部分性地或完全地進行反應,亦可未反應。另外,可為藉由熱等而硬化的狀態,亦可為不硬化的狀態。The adhesive layer will not be specifically limited as long as the peeling force with an electromagnetic wave shielding sheet falls within the said range. For example, a layer containing an adhesive such as a silicone adhesive, an acrylic adhesive, a rubber adhesive, or a urethane adhesive is exemplified. The adhesive contained in the adhesive layer may be single type, or may be 2 or more types. In the present invention, the adhesive contained in the adhesive layer may partially or completely react, or may not react. In addition, it may be in a state cured by heat or the like, or may be in a non-cured state.

(1)矽酮系黏著劑 本說明書中矽酮系黏著劑是指將矽酮聚合物設為基礎聚合物(聚合物成分中的主成分,即佔聚合物成分整體的50質量%以上的成分)的黏著劑。 矽酮系黏著劑就以下觀點而言有利:可相對地降低剝離力而電磁波遮蔽片容易自黏著層剝離、可抑制對電磁波遮蔽片的殘膠(黏著劑的殘存)等。作為矽酮系黏著劑,可列舉加成反應型矽酮系黏著劑、過氧化物硬化型矽酮系黏著劑、縮合型矽酮系黏著劑等。就於硬化反應中不使用過氧化物,不產生分解物的觀點而言,較佳為加成反應型矽酮系黏著劑。(1) Silicone-based adhesives Silicone-based adhesives in this specification refer to silicone polymers as the base polymer (the main component of the polymer component, that is, a component that accounts for 50% by mass or more of the entire polymer component ) adhesive. Silicone-based adhesives are advantageous in that the peeling force can be relatively reduced, the electromagnetic wave shielding sheet can be easily peeled off from the adhesive layer, and the adhesive residue on the electromagnetic wave shielding sheet (residue of the adhesive) can be suppressed. Examples of the silicone adhesive include an addition reaction type silicone adhesive, a peroxide-curable silicone adhesive, a condensation type silicone adhesive, and the like. From the viewpoint of not using a peroxide in the curing reaction and generating no decomposition product, an addition reaction type silicone-based adhesive is preferable.

(加成反應型矽酮系黏著劑) 所謂加成反應型矽酮系黏著劑,為含有加成反應型矽酮樹脂與矽酮樹脂(resin)的矽酮系黏著劑,所述加成反應型矽酮樹脂包含在一分子中具有至少兩個烯基(可列舉乙烯基、烯丙基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基等一價烴基,其中特佳為乙烯基)的第1聚二甲基矽氧烷、以及在一分子中具有至少兩個氫矽烷基的第2聚二甲基矽氧烷。(Addition Reaction Type Silicone Adhesive) The so-called addition reaction type silicone adhesive is a silicone adhesive containing an addition reaction type silicone resin and a silicone resin (resin). Type silicone resin contains at least two alkenyl groups in one molecule (such as vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, etc.) The first polydimethylsiloxane having a hydrocarbon group, particularly preferably a vinyl group), and the second polydimethylsiloxane having at least two hydrosilyl groups in one molecule.

第1聚二甲基矽氧烷中的烯基的含有率(烯基的個數相對於矽氧烷鍵的個數的比例)較佳為0.01%~10%,更佳為0.1%~5%。烯基較佳為至少存在於分子鏈的兩末端,更佳為存在於兩末端與側鏈。第1聚二甲基矽氧烷的聚合度(矽氧烷鍵的個數)較佳為200~5,000,更佳為500~3,000。 第1聚二甲基矽氧烷的重量平均分子量較佳為20,000~1,300,000,更佳為300,000~1,200,000。The alkenyl group content in the first polydimethylsiloxane (the ratio of the number of alkenyl groups to the number of siloxane bonds) is preferably 0.01% to 10%, more preferably 0.1% to 5%. %. The alkenyl group is preferably present at least at both terminals of the molecular chain, more preferably present at both terminals and side chains. The degree of polymerization (the number of siloxane bonds) of the first polydimethylsiloxane is preferably from 200 to 5,000, more preferably from 500 to 3,000. The weight average molecular weight of the first polydimethylsiloxane is preferably from 20,000 to 1,300,000, more preferably from 300,000 to 1,200,000.

本說明書中聚合物的分子量(重量平均分子量及數量平均分子量)為利用凝膠滲透層析(Gel Permeation Chromatography,GPC)法而測定的聚苯乙烯換算的值。The molecular weight (weight average molecular weight and number average molecular weight) of a polymer in this specification is a polystyrene conversion value measured by the gel permeation chromatography (Gel Permeation Chromatography, GPC) method.

第2聚二甲基矽氧烷中的氫矽烷基的含量較佳為於一分子中為2個~300個,更佳為4個~200個。第2聚二甲基矽氧烷的聚合度(矽氧烷鍵的個數)較佳為50~2,000,更佳為100~1,500。The content of the hydrosilyl groups in the second polydimethylsiloxane is preferably from 2 to 300 per molecule, more preferably from 4 to 200. The degree of polymerization (the number of siloxane bonds) of the second polydimethylsiloxane is preferably from 50 to 2,000, more preferably from 100 to 1,500.

加成反應型矽酮樹脂中,第1聚二甲基矽氧烷與第2聚二甲基矽氧烷的比率例如較佳為相對於第1聚二甲基矽氧烷100質量份而言的第2聚二甲基矽氧烷的調配比為0.01質量份~20質量份,更佳為0.1質量份~10質量份。In the addition reaction type silicone resin, the ratio of the first polydimethylsiloxane to the second polydimethylsiloxane is preferably, for example, relative to 100 parts by mass of the first polydimethylsiloxane The blending ratio of the second polydimethylsiloxane is 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass.

若第1聚二甲基矽氧烷中所含的烯基的含量、第2聚二甲基矽氧烷中所含的氫矽烷基的含量、及第2聚二甲基矽氧烷相對於第1聚二甲基矽氧烷的調配比分別為所述範圍內,則有使第1聚二甲基矽氧烷與第2聚二甲基矽氧烷的加成反應良好地進行的傾向。此外,第1聚二甲基矽氧烷較佳為不具有氫矽烷基,第2聚二甲基矽氧烷較佳為不具有烯基。If the content of the alkenyl group contained in the first polydimethylsiloxane, the content of the hydrosilyl group contained in the second polydimethylsiloxane, and the second polydimethylsiloxane relative to When the compounding ratio of the first polydimethylsiloxane is within the above-mentioned ranges, the addition reaction between the first polydimethylsiloxane and the second polydimethylsiloxane tends to progress favorably. . Moreover, it is preferable that the 1st polydimethylsiloxane does not have a hydrosilyl group, and it is preferable that a 2nd polydimethylsiloxane does not have an alkenyl group.

矽酮樹脂具有對矽酮系黏著劑賦予黏著性的作用。本說明書中所謂矽酮樹脂,是指具有三維網眼結構的矽酮。 作為矽酮樹脂,例如可列舉包含作為一官能矽氧烷單元[(CH3 )3 SiO1/2 ]的M單元、與作為四官能矽氧烷單元[SiO4/2 ]的Q單元的MQ樹脂。MQ樹脂中M單元與Q單元的莫耳比(M單元/Q單元)較佳為0.6~1.7。The silicone resin has the function of imparting adhesiveness to the silicone-based adhesive. The silicone resin used in this specification refers to silicone having a three-dimensional network structure. Examples of the silicone resin include MQ, which includes an M unit as a monofunctional siloxane unit [(CH 3 ) 3 SiO 1/2 ] and a Q unit as a tetrafunctional siloxane unit [SiO 4/2 ]. resin. The molar ratio of the M unit to the Q unit (M unit/Q unit) in the MQ resin is preferably 0.6-1.7.

加成反應型矽酮系黏著劑中,相對於加成反應型矽酮樹脂100質量份而言的矽酮樹脂的調配比較佳為1質量份~30質量份,更佳為3質量份~20質量份,進而佳為5質量份~15質量份。藉由矽酮樹脂的調配比處於所述範圍,可將加成反應型矽酮系黏著劑的剝離性調整為理想的範圍。即,有電磁波遮蔽片更容易地自使用加成反應型矽酮系黏著劑而獲得的黏著層剝離、更不易產生對電磁波遮蔽片的殘膠的傾向。In the addition reaction type silicone adhesive, the blending ratio of the silicone resin is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the addition reaction type silicone resin. parts by mass, more preferably 5 to 15 parts by mass. When the blending ratio of the silicone resin is in the above range, the peelability of the addition reaction type silicone adhesive can be adjusted to a desired range. That is, the electromagnetic wave shielding sheet tends to be more easily peeled from the adhesive layer obtained by using the addition reaction type silicone-based adhesive, and the residue of the electromagnetic wave shielding sheet tends to be less likely to be generated.

加成反應型矽酮系黏著劑較佳為含有觸媒。藉由含有觸媒,可效率更良好地進行加成反應型矽酮樹脂的硬化反應。觸媒只要為可使第1聚二甲基矽氧烷與第2聚二甲基矽氧烷進行加成反應者,則並無特別限定,其中較佳為包含鉑族金屬的化合物。作為包含鉑族金屬的化合物,可列舉:微粒子狀鉑、吸附於碳粉末載體上的微粒子狀鉑、氯鉑酸、醇改質氯鉑酸、氯鉑酸的烯烴錯合物、鈀、銠等。The addition reaction type silicone-based adhesive preferably contains a catalyst. By containing the catalyst, the curing reaction of the addition reaction type silicone resin can be performed more efficiently. The catalyst is not particularly limited as long as it can cause the addition reaction of the first polydimethylsiloxane and the second polydimethylsiloxane, but a compound containing a platinum group metal is preferable among them. Examples of compounds containing platinum group metals include: fine-particulate platinum, fine-particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, palladium, rhodium Wait.

於加成反應型矽酮系黏著劑包含觸媒的情況下,相對於加成反應型矽酮樹脂100質量份而言的觸媒的調配量(於觸媒為包含鉑族金屬的化合物的情況下,相當於鉑族金屬的量)較佳為0.0001質量份~0.1質量份,更佳為0.001質量份~0.01質量份。When the addition reaction type silicone adhesive contains a catalyst, the compounding amount of the catalyst relative to 100 parts by mass of the addition reaction type silicone resin (when the catalyst is a compound containing a platinum group metal , the amount corresponding to the platinum group metal) is preferably 0.0001 to 0.1 parts by mass, more preferably 0.001 to 0.01 parts by mass.

(過氧化物硬化型矽酮系黏著劑及縮合型矽酮系黏著劑) 過氧化物硬化型矽酮系黏著劑一般為藉由過氧化物而使有機聚矽氧烷硬化(交聯)並生成矽酮系聚合物的黏著劑。另外,縮合型矽酮系黏著劑一般為藉由在末端具有矽烷醇基或烷氧基矽烷基等水解性矽烷基的聚有機矽氧烷間的脫水或脫醇反應而生成矽酮系聚合物的黏著劑。(Peroxide Curable Silicone Adhesive and Condensation Silicone Adhesive) Peroxide curable silicone adhesive is generally made by curing (crosslinking) organopolysiloxane with peroxide and Produces adhesives for silicone-based polymers. In addition, condensation-type silicone-based adhesives generally form silicone-based polymers by dehydration or dealcoholization reactions between polyorganosiloxanes having hydrolyzable silanyl groups such as silanol groups or alkoxysilyl groups at the ends. of adhesives.

於過氧化物硬化型矽酮系黏著劑的情況下,使用至少具有甲基的矽酮橡膠,於縮合型矽酮系黏著劑的情況下,使用在末端具有矽烷醇基或水解性烷氧基矽烷基的矽酮橡膠。此外,矽酮橡膠中的有機聚矽氧烷的重量平均分子量通常為15萬以上,較佳為28萬~100萬,更佳為50萬~90萬。In the case of a peroxide-curing silicone adhesive, use a silicone rubber having at least a methyl group, and in the case of a condensation-type silicone adhesive, use a silicone rubber having a silanol group or a hydrolyzable alkoxy group at the end. Silane-based silicone rubber. In addition, the weight average molecular weight of the organopolysiloxane in the silicone rubber is usually 150,000 or more, preferably 280,000 to 1 million, more preferably 500,000 to 900,000.

矽酮系黏著劑除聚合物成分以外,亦可包含反應抑制劑、密接提昇劑等各種添加劑。Silicone-based adhesives may contain various additives such as reaction inhibitors and adhesion enhancers in addition to polymer components.

使用矽酮系黏著劑而於基材上形成黏著層的方法並無特別限制。例如,可將矽酮系黏著劑賦予至基材上,並視需要進行乾燥、硬化,藉此形成黏著層。賦予例如可使用棒塗機、模塗機、凹版塗佈機、輥塗機、刮刀式塗佈機等塗敷機來進行。The method of forming the adhesive layer on the substrate using the silicone adhesive is not particularly limited. For example, an adhesive layer can be formed by applying a silicone-based adhesive to the base material, drying and hardening as necessary. The application can be performed using, for example, a coating machine such as a bar coater, a die coater, a gravure coater, a roll coater, or a knife coater.

於矽酮系黏著劑包含稀釋劑的情況下,稀釋劑並無特別限制。例如可列舉:甲苯、己烷、庚烷等烴化合物,丙酮、乙酸乙酯、甲基乙基酮、甲基異丁基酮等。矽酮系黏著劑中所含的稀釋劑可為單獨一種,亦可為兩種以上。When the silicone-based adhesive contains a diluent, the diluent is not particularly limited. For example, hydrocarbon compounds, such as toluene, hexane, and heptane, acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned. The diluent contained in the silicone-based adhesive may be a single type or two or more types.

於矽酮系黏著劑為加成反應型矽酮黏著劑的情況下,較佳為將加成反應型矽酮黏著劑賦予至基材上後進行加熱並硬化。該情況下的加熱溫度較佳為80℃~180℃,加熱時間較佳為10秒~90秒左右。When the silicone-based adhesive is an addition-reaction type silicone adhesive, it is preferable to apply the addition-reaction type silicone adhesive to the substrate and then heat and harden it. In this case, the heating temperature is preferably from 80°C to 180°C, and the heating time is preferably from about 10 seconds to 90 seconds.

(2)丙烯酸系黏著劑 本說明書中所謂丙烯酸系黏著劑,是指將丙烯酸系聚合物設為基礎聚合物的黏著劑。所謂丙烯酸系聚合物,是指將於一分子中具有至少一個(甲基)丙烯醯基的單體(以下,有時將其稱為「丙烯酸系單體」)設為主要的構成單量體成分(佔構成丙烯酸系聚合物的單體總量中的50質量%以上的成分)的聚合物。丙烯酸系黏著劑就透明性、耐候性、耐熱性、耐溶劑性等方面而言有利。(2) Acrylic adhesive The acrylic adhesive used in this specification refers to an adhesive in which an acrylic polymer is used as a base polymer. The term "acrylic polymer" refers to a monomer having at least one (meth)acryl group in one molecule (hereinafter, sometimes referred to as "acrylic monomer") as the main constituent monomer. Components (components accounting for 50% by mass or more of the total monomers constituting the acrylic polymer). Acrylic adhesives are advantageous in terms of transparency, weather resistance, heat resistance, solvent resistance, and the like.

於設計丙烯酸系黏著劑中所含的丙烯酸系聚合物時,重要的是考慮玻璃轉移點(相對於黏附體的黏著性、能夠應用的溫度等)、交聯點的導入(耐久性、耐熱性等)、丙烯酸系單體的共聚性(丙烯酸系聚合物的分子結構、交聯點等的均勻性)等而調節單體的種類、分子量等。為了於分子中導入交聯點,使用含有能夠與併用的交聯劑反應的官能基的單體(丙烯酸、丙烯酸羥基乙酯等)來合成丙烯酸系聚合物。When designing the acrylic polymer contained in the acrylic adhesive, it is important to consider the glass transition point (adhesion to the adherend, applicable temperature, etc.), the introduction of the cross-linking point (durability, heat resistance etc.), copolymerization of acrylic monomers (molecular structure of acrylic polymers, uniformity of cross-linking points, etc.), etc. to adjust the type, molecular weight, etc. of the monomers. In order to introduce crosslinking points into the molecule, an acrylic polymer is synthesized using a monomer (acrylic acid, hydroxyethyl acrylate, etc.) containing a functional group capable of reacting with a crosslinking agent used in combination.

作為丙烯酸系聚合物,可列舉將(甲基)丙烯酸烷基酯設為主要的構成單量體成分的聚合物。作為(甲基)丙烯酸烷基酯,例如可較佳地使用下述式(1)所表示的化合物。 CH2 =C(R1 )COOR2 (1)Examples of the acrylic polymer include polymers in which an alkyl (meth)acrylate is used as a main constituent monomer component. As the alkyl (meth)acrylate, for example, a compound represented by the following formula (1) can be preferably used. CH 2 =C(R 1 )COOR 2 (1)

此處,所述式(1)中的R1 表示氫原子或甲基,R2 表示碳原子數1~20的烷基(可為鏈狀烷基或脂環式烷基的任一種)。Here, R 1 in the formula (1) represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 20 carbon atoms (which may be either a chain alkyl group or an alicyclic alkyl group).

就獲得黏著性能優異的黏著劑的觀點而言,R2 較佳為碳原子數2~14(C2~14)的鏈狀烷基(可為直鏈狀烷基或分支狀烷基的任一種)。作為C2~14的鏈狀烷基,可列舉:乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、新戊基、正己基、正庚基、正辛基、異辛基、2-乙基己基、正壬基、異壬基、正癸基、異癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基等。作為R2 為脂環式烷基的情況下的脂環式烷基,可列舉環己基、異冰片基等。From the viewpoint of obtaining an adhesive with excellent adhesive performance, R2 is preferably a chained alkyl group with 2 to 14 carbon atoms (C2 to 14) (it can be either a straight chained alkyl group or a branched alkyl group) ). Examples of C2-14 chain alkyl groups include ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-pentyl, isopentyl, Neopentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, n-dodecyl Alkyl, n-tridecyl, n-tetradecyl, etc. Examples of the alicyclic alkyl group in the case where R 2 is an alicyclic alkyl group include cyclohexyl, isobornyl and the like.

就獲得黏著性能更優異的丙烯酸系聚合物的觀點而言,丙烯酸系聚合物的合成中使用的單體總量中的50質量%以上(例如,50質量%~99.9質量%)、更佳為70質量%以上(例如,70質量%~99.9質量%)、進而佳為85質量%以上(例如,85質量%~99.9質量%)較佳為於所述式(1)中R2 為C2~14的鏈狀烷基的(甲基)丙烯酸酯,更佳為R2 為C4~10的鏈狀烷基丙烯酸酯,進而佳為選自丙烯酸正丁酯及丙烯酸2-乙基己酯中的至少一種。From the viewpoint of obtaining an acrylic polymer with better adhesive performance, 50% by mass or more (for example, 50% by mass to 99.9% by mass) of the total amount of monomers used in the synthesis of the acrylic polymer, more preferably 70% by mass or more (for example, 70% by mass to 99.9% by mass), more preferably 85% by mass or more (for example, 85% by mass to 99.9% by mass), preferably R 2 in the formula (1) is C2 to 14 chain alkyl (meth)acrylate, more preferably R2 is a chain alkyl acrylate of C4~10, and more preferably selected from n-butyl acrylate and 2 -ethylhexyl acrylate at least one.

丙烯酸系聚合物較佳為具有羥基作為交聯點。作為具有羥基的丙烯酸系聚合物,可較佳地使用在聚合成分中包含含有羥基的丙烯酸系單體者。The acrylic polymer preferably has a hydroxyl group as a crosslinking point. As an acrylic polymer which has a hydroxyl group, what contains a hydroxyl group containing acrylic monomer in a polymerization component can be used preferably.

作為含有羥基的丙烯酸系單體的具體例,可列舉:(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基己酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(4-羥基甲基環己基)甲基丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、N-羥基乙基(甲基)丙烯醯胺、N-羥基丙基(甲基)丙烯醯胺等。含有羥基的丙烯酸系單體可單獨使用一種,亦可組合使用兩種以上。Specific examples of hydroxyl-containing acrylic monomers include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylate Base) 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyl (meth)acrylate Octyl ester, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methacrylate, polypropylene glycol mono(meth)acrylate, N -Hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, etc. The hydroxyl group-containing acrylic monomer may be used alone or in combination of two or more.

含有羥基的丙烯酸系單體中,較佳為含有羥基的(甲基)丙烯酸酯。含有羥基的(甲基)丙烯酸酯較佳為(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等。Among hydroxyl group-containing acrylic monomers, hydroxyl group-containing (meth)acrylates are preferred. The (meth)acrylate containing hydroxyl group is preferably 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid 2-Hydroxybutyl, 4-Hydroxybutyl (meth)acrylate, etc.

關於具有羥基的丙烯酸系聚合物,用於其合成的單體總量中含有羥基的丙烯酸系單體的比例例如可為0.01質量%~20質量%的範圍,較佳為0.05質量%~15質量%的範圍,更佳為0.1質量%~10質量%的範圍。Regarding the acrylic polymer having a hydroxyl group, the proportion of the acrylic monomer containing a hydroxyl group in the total amount of monomers used for its synthesis may be, for example, in the range of 0.01% by mass to 20% by mass, preferably 0.05% by mass to 15% by mass. %, more preferably in the range of 0.1% by mass to 10% by mass.

丙烯酸系聚合物亦可包含具有羥基以外的官能基的丙烯酸系單體及丙烯酸系單體以外的單體(以下,亦稱為其他單體)作為聚合成分。其他單體例如可出於調整丙烯酸系聚合物的Tg、黏著性能等等的目的而使用。例如,作為可提高黏著劑的凝聚力與耐熱性的單體,可列舉:含磺酸基的單體、含磷酸基的單體、含氰基的單體、乙烯酯類、芳香族乙烯基化合物等。另外,作為向丙烯酸系聚合物中導入可成為交聯點的官能基、或可有助於接著力的提高的單體,可列舉:含羧基的單體、含酸酐基的單體、含醯胺基的單體、含胺基的單體、含醯亞胺基的單體、含環氧基的單體、(甲基)丙烯醯基嗎啉、乙烯醚類等。其他單體可單獨使用一種,亦可組合使用兩種以上。 The acrylic polymer may contain, as a polymerization component, an acrylic monomer having a functional group other than a hydroxyl group and a monomer other than the acrylic monomer (hereinafter also referred to as another monomer). Other monomers may be used, for example, for the purpose of adjusting Tg, adhesive properties, etc. of the acrylic polymer. For example, monomers that can improve the cohesion and heat resistance of adhesives include: sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, cyano group-containing monomers, vinyl esters, aromatic vinyl compounds Wait. In addition, examples of monomers that introduce functional groups that can serve as crosslinking points into acrylic polymers or contribute to the improvement of adhesive force include carboxyl group-containing monomers, acid anhydride group-containing monomers, acyl-containing Amine-based monomers, amine-containing monomers, imide-containing monomers, epoxy-containing monomers, (meth)acrylmorpholine, vinyl ethers, etc. The other monomers may be used alone or in combination of two or more.

作為含磺酸基的單體,可列舉:苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺基丙酯、(甲基)丙烯醯氧基萘磺酸、乙烯基磺酸鈉等。 Examples of sulfonic acid group-containing monomers include: styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid, sodium vinylsulfonate, etc.

作為含磷酸基的單體,可列舉2-羥基乙基丙烯醯基磷酸酯等。 As a monomer containing a phosphoric acid group, 2-hydroxyethyl acryloyl phosphate etc. are mentioned.

作為含氰基的單體,可列舉丙烯腈、甲基丙烯腈等。 As a cyano group-containing monomer, acrylonitrile, methacrylonitrile, etc. are mentioned.

作為乙烯酯類,可列舉:乙酸乙烯酯、丙酸乙烯酯、月桂酸乙烯酯等。 Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl laurate, and the like.

作為芳香族乙烯基化合物,可列舉:苯乙烯、取代苯乙烯(氯苯乙烯、氯甲基苯乙烯、α-甲基苯乙烯等)等。 Examples of the aromatic vinyl compound include styrene, substituted styrenes (chlorostyrene, chloromethylstyrene, α-methylstyrene, etc.), and the like.

作為含羧基的單體,可列舉:丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、衣康酸、馬來酸、富馬酸、丁烯酸、異丁烯酸等。 Examples of carboxyl group-containing monomers include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, Methacrylate, etc.

作為含酸酐基的單體,可列舉:馬來酸酐、衣康酸酐、所述含羧基的單體的酸酐等。 作為含醯胺基的單體,可列舉:丙烯醯胺、甲基丙烯醯胺、二乙基丙烯醯胺、N-乙烯基吡咯啶酮、N,N-二甲基丙烯醯胺、N,N-二甲基甲基丙烯醯胺、N,N-二乙基丙烯醯胺、N,N-二乙基甲基丙烯醯胺、N,N'-亞甲基雙丙烯醯胺、N,N-二甲基胺基丙基丙烯醯胺、N,N-二甲基胺基丙基甲基丙烯醯胺、二丙酮丙烯醯胺等。 作為含胺基的單體,可列舉:(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基丙酯等。 作為含醯亞胺基的單體,可列舉:環己基馬來醯亞胺、異丙基馬來醯亞胺、N-環己基馬來醯亞胺、衣康醯亞胺等。 作為含環氧基的單體,可列舉:(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸甲基縮水甘油酯、烯丙基縮水甘油醚等。 作為乙烯醚類,可列舉:甲基乙烯醚、乙基乙烯醚、異丁基乙烯醚等。Examples of the acid anhydride group-containing monomer include maleic anhydride, itaconic anhydride, acid anhydrides of the above-mentioned carboxyl group-containing monomer, and the like. Examples of amide group-containing monomers include: acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N,N-dimethylacrylamide, N, N-Dimethylmethacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide, N,N'-methylenebisacrylamide, N, N-dimethylaminopropyl acrylamide, N,N-dimethylaminopropyl methacrylamide, diacetone acrylamide, etc. Examples of amino group-containing monomers include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethyl (meth)acrylate Aminopropyl Etc. Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, itaconimide, and the like. Glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, allyl glycidyl ether, etc. are mentioned as an epoxy group containing monomer. Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.

於丙烯酸系聚合物包含其他單體作為聚合成分的情況下,其他單體的含有率較佳為其他單體的合計為用於丙烯酸系聚合物的合成的單體總量中的40質量%以下,更佳為30質量%以下。另外,較佳為其他單體的合計為用於丙烯酸系聚合物的合成的單體總量中的0.001質量%以上。When the acrylic polymer contains other monomers as polymerization components, the content of other monomers is preferably 40% by mass or less of the total amount of monomers used in the synthesis of the acrylic polymer. , more preferably 30% by mass or less. Moreover, it is preferable that the sum total of other monomers is 0.001 mass % or more in the monomer total amount used for the synthesis|combination of an acryl-type polymer.

丙烯酸系聚合物亦可為僅將丙烯酸系單體設為聚合成分者。作為僅將丙烯酸系單體設為聚合成分的丙烯酸系聚合物,例如可列舉僅將碳數為6~14的(甲基)丙烯酸烷基酯設為聚合成分的丙烯酸系聚合物、僅將碳數為6~14的(甲基)丙烯酸烷基酯與含羥基的(甲基)丙烯酸酯設為聚合成分的丙烯酸系聚合物等。As an acrylic polymer, what used only an acrylic monomer as a polymerization component may be sufficient. Examples of acrylic polymers containing only acrylic monomers as polymerization components include acrylic polymers containing only alkyl (meth)acrylates having 6 to 14 carbon atoms as polymerization components, An acrylic polymer or the like in which an alkyl (meth)acrylate having a number of 6 to 14 and a hydroxyl group-containing (meth)acrylate are polymerized components.

丙烯酸系聚合物的藉由凝膠滲透層析法(GPC)而獲得的標準聚苯乙烯換算的重量平均分子量(Mw)例如可為20´104 以上,較佳為30´104 以上。另外,例如可為90´104 以下,較佳為80´104 以下。若丙烯酸系聚合物的重量平均分子量為所述範圍內,則有可獲得顯示出良好的黏著性能的黏著劑的傾向。The standard polystyrene-equivalent weight average molecular weight (Mw) of the acrylic polymer obtained by gel permeation chromatography (GPC) may be, for example, 20×10 4 or more, preferably 30×10 4 or more. Also, for example, it may be 90´10 4 or less, preferably 80´10 4 or less. There exists a tendency for the adhesive agent which shows favorable adhesive performance to be obtained as the weight average molecular weight of an acryl-type polymer exists in the said range.

丙烯酸系聚合物可為無規共聚物,亦可為嵌段共聚物,抑或可為接枝共聚物等。就生產性等觀點而言,較佳為通常為無規共聚物。The acrylic polymer may be a random copolymer, a block copolymer, or a graft copolymer. From the viewpoint of productivity and the like, a random copolymer is usually preferred.

丙烯酸系聚合物的玻璃轉移溫度(Tg)較佳為-15℃以下,更佳為-25℃以下,進而佳為-40℃以下。另外,玻璃轉移溫度(Tg)較佳為-70℃以上。若丙烯酸系聚合物的玻璃轉移溫度(Tg)為所述範圍,則有可形成顯示出良好的黏著性能的黏著劑的傾向。The glass transition temperature (Tg) of the acrylic polymer is preferably -15°C or lower, more preferably -25°C or lower, further preferably -40°C or lower. In addition, the glass transition temperature (Tg) is preferably -70°C or higher. When the glass transition temperature (Tg) of an acryl-type polymer exists in the said range, it exists in the tendency for the adhesive agent which shows favorable adhesive performance to be formed.

本說明書中所謂丙烯酸系聚合物的Tg,是指基於構成丙烯酸系聚合物的各單體的均聚物(homopolymer)的Tg、與該單體的質量分率(質量基準的共聚比例)並根據佛克斯(Fox)的式子而求出的值。因而,丙烯酸系聚合物的Tg可藉由適宜改變單體組成(即,用於丙烯酸系聚合物的合成的單體種類、使用量比等)而調整。此處,作為均聚物的Tg,採用公知資料中記載(「聚合物手冊(Polymer Handbook)」(第3版,約翰・威利父子股份有限公司(John Wiley & Sons, Inc)1989年))的值。作為所述均聚物的Tg,具體而言使用以下的值。The Tg of the acrylic polymer used in this specification refers to the Tg of the homopolymer (homopolymer) based on each monomer constituting the acrylic polymer, and the mass fraction of the monomer (copolymerization ratio on a mass basis) based on The value obtained from the formula of Fox. Therefore, the Tg of the acrylic polymer can be adjusted by appropriately changing the monomer composition (that is, the type of monomer used in the synthesis of the acrylic polymer, the ratio of the amount used, and the like). Here, as the Tg of the homopolymer, that described in a known material ("Polymer Handbook" (3rd edition, John Wiley & Sons, Inc, 1989)) is used. value. As the Tg of the homopolymer, specifically, the following values are used.

丙烯酸2-乙基己酯的均聚物:-70℃ 丙烯酸正丁酯的均聚物:-55℃ 丙烯酸乙酯的均聚物:-22℃ 丙烯酸甲酯的均聚物:8℃ 甲基丙烯酸甲酯的均聚物:105℃ 甲基丙烯酸環己酯的均聚物:66℃ 乙酸乙烯酯的均聚物:32℃ 苯乙烯的均聚物:100℃ 丙烯酸的均聚物:106℃ 甲基丙烯酸的均聚物:130℃Homopolymer of 2-ethylhexyl acrylate: -70°C Homopolymer of n-butyl acrylate: -55°C Homopolymer of ethyl acrylate: -22°C Homopolymer of methyl acrylate: 8°C Methyl Homopolymer of methyl acrylate: 105°C Homopolymer of cyclohexyl methacrylate: 66°C Homopolymer of vinyl acetate: 32°C Homopolymer of styrene: 100°C Homopolymer of acrylic acid: 106°C Homopolymer of methacrylic acid: 130°C

「聚合物手冊(Polymer Handbook)」中未記載的均聚物的Tg是使用利用下述方法而測定的值。 向具備溫度計、攪拌機、氮氣導入管及回流冷卻管的反應器中投入單體100質量份、偶氮雙異丁腈0.2質量份、及作為聚合溶媒的乙酸乙酯200質量份,一面使氮氣流通一面於室溫(25℃)下攪拌1小時。如此去除聚合體系內的氧後,昇溫至63℃並反應10小時。繼而,冷卻至室溫(25℃)為止,獲得固體成分濃度為33質量%的均聚物溶液。繼而,將該均聚物溶液流延塗佈至剝離襯墊(release liner)上,進行乾燥而製作厚度約2 mm的試驗樣品(片狀均聚物)。將該試驗樣品衝壓成直徑7.9 mm的圓盤狀,並利用平行板夾入,使用黏彈性試驗機(ARES,流變(Rheometrics)公司)賦予頻率1 Hz的剪切應變,並以溫度範圍-70℃~150℃、5℃/min的昇溫速度藉由剪切模式來測定黏彈性,從而將tanδ的峰頂溫度設為均聚物的Tg。Tg of a homopolymer not described in "Polymer Handbook" is a value measured by the following method. 100 parts by mass of monomers, 0.2 parts by mass of azobisisobutyronitrile, and 200 parts by mass of ethyl acetate as a polymerization solvent were charged into a reactor equipped with a thermometer, a stirrer, a nitrogen gas introduction pipe, and a reflux cooling pipe, and nitrogen gas was circulated. Stir at room temperature (25°C) for 1 hour. After removing oxygen in the polymerization system in this way, the temperature was raised to 63° C., and the reaction was carried out for 10 hours. Then, it cooled to room temperature (25 degreeC), and the homopolymer solution whose solid content concentration was 33 mass % was obtained. Next, this homopolymer solution was cast-coated on a release liner (release liner), and dried to prepare a test sample (sheet-shaped homopolymer) having a thickness of about 2 mm. The test sample was punched into a disc shape with a diameter of 7.9 mm, and clamped by a parallel plate, and a viscoelasticity testing machine (ARES, Rheometrics) was used to impart a shear strain at a frequency of 1 Hz, and the temperature range - Viscoelasticity was measured in a shear mode at a heating rate of 70°C to 150°C and 5°C/min, and the peak top temperature of tan δ was defined as the Tg of the homopolymer.

合成丙烯酸系聚合物的方法並無特別限定,可應用溶液聚合法、乳化聚合法、塊狀聚合法、懸浮聚合法等一般使用的方法。就包含丙烯酸系聚合物的溶劑型黏著劑組成物的製備容易度的觀點而言,較佳為溶液聚合法。溶液聚合法中所使用的有機溶媒(聚合溶媒)並無特別限制,可列舉:甲苯、乙酸乙酯、己烷、環己烷等。所使用的有機溶媒可為單獨一種,亦可為兩種以上。The method for synthesizing the acrylic polymer is not particularly limited, and generally used methods such as solution polymerization, emulsion polymerization, block polymerization, and suspension polymerization can be applied. From the viewpoint of easiness of preparation of a solvent-based adhesive composition containing an acrylic polymer, a solution polymerization method is preferable. The organic solvent (polymerization vehicle) used in the solution polymerization method is not particularly limited, and examples thereof include toluene, ethyl acetate, hexane, and cyclohexane. The organic solvent used may be single type, or may be two or more types.

本說明書中所謂溶劑型黏著劑組成物,是指於有機溶媒中包含黏著成分的形態的組成物。有機溶媒並無特別限制。例如可列舉:甲苯、二甲苯、乙酸乙酯、己烷、環己烷、甲基環己烷、異丙基醇等。有機溶媒可為單獨一種,亦可為兩種以上。溶劑型黏著劑組成物較佳為其非揮發成分(Non-Volatile,NV)為整體的30質量%~60質量%,更佳為30質量%~50質量%。溶劑型黏著劑組成物的黏度較佳為3 Pa・s~25 Pa・s,更佳為5 Pa・s~15 Pa・s。此外,所述黏度是指於23℃的環境下使用旋轉黏度計而測定的值。The term "solvent-type adhesive composition" in this specification refers to a composition in the form of an adhesive component contained in an organic solvent. The organic solvent is not particularly limited. For example, toluene, xylene, ethyl acetate, hexane, cyclohexane, methylcyclohexane, isopropyl alcohol, etc. are mentioned. An organic solvent may be used alone or in combination of two or more. The solvent-based adhesive composition preferably has a non-volatile component (Non-Volatile, NV) of 30% to 60% by mass, more preferably 30% to 50% by mass. The viscosity of the solvent-based adhesive composition is preferably from 3 Pa・s to 25 Pa・s, more preferably from 5 Pa・s to 15 Pa・s. In addition, the said viscosity means the value measured using the rotational viscometer in 23 degreeC environment.

丙烯酸系黏著劑可以丙烯酸系聚合物進行交聯的方式進行設計。作為使丙烯酸系聚合物交聯的具體方法,可列舉如下方法:藉由於丙烯酸系聚合物的聚合成分中包含具有可成為交聯點的官能基(羥基、羧基等)的單體,將官能基導入至丙烯酸系聚合物中,並將可與該官能基反應而形成交聯結構的化合物(交聯劑)添加至丙烯酸系聚合物中來進行反應。Acrylic adhesives can be engineered in such a way that acrylic polymers are cross-linked. As a specific method of crosslinking an acrylic polymer, a method may be mentioned in which a monomer having a functional group (hydroxyl group, carboxyl group, etc.) It is introduced into an acrylic polymer, and a compound (crosslinking agent) capable of reacting with the functional group to form a crosslinked structure is added to the acrylic polymer to react.

交聯劑並無特別限制,可選自用於丙烯酸系聚合物的交聯的一般的化合物中。例如可列舉:環氧系交聯劑、異氰酸酯系交聯劑、三聚氰胺系交聯劑、過氧化物系交聯劑、金屬烷氧化物系交聯劑、金屬螯合物系交聯劑、金屬鹽系交聯劑、碳二醯亞胺系交聯劑、噁唑啉系交聯劑、氮丙啶系交聯劑、胺系交聯劑等,其中較佳為環氧系交聯劑與異氰酸酯系交聯劑。所使用的交聯劑可為單獨一種,亦可為兩種以上。The crosslinking agent is not particularly limited, and may be selected from general compounds used for crosslinking acrylic polymers. For example, epoxy-based cross-linking agents, isocyanate-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, metal Salt-based cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, amine-based cross-linking agents, etc., wherein epoxy-based cross-linking agents and Isocyanate-based crosslinking agent. The crosslinking agent used may be one kind alone, or two or more kinds thereof.

作為環氧系交聯劑,可列舉:N,N,N',N'-四縮水甘油基-間二甲苯二胺、二縮水甘油基苯胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、1,6-己二醇二縮水甘油醚、新戊二醇二縮水甘油醚、乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、山梨糖醇聚縮水甘油醚、丙三醇聚縮水甘油醚、季戊四醇聚縮水甘油醚、聚丙三醇聚縮水甘油醚、山梨糖醇酐聚縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、己二酸二縮水甘油酯、鄰-鄰苯二甲酸二縮水甘油酯、三縮水甘油基-三(2-羥基乙基)異氰脲酸酯、間苯二酚二縮水甘油醚、雙酚-S-二縮水甘油醚、於分子內具有兩個以上環氧基的環氧樹脂等。Examples of epoxy-based crosslinking agents include: N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidyl aniline, 1,3-bis(N,N-diglycidyl Glycerylaminomethyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol Diglycidyl ether, Polypropylene glycol diglycidyl ether, Sorbitol polyglycidyl ether, Glycerol polyglycidyl ether, Pentaerythritol polyglycidyl ether, Polyglycerol polyglycidyl ether, Sorbitan polyglycidyl ether , trimethylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl o-phthalate, triglycidyl-tris(2-hydroxyethyl) isocyanurate, m- Hydroquinone diglycidyl ether, bisphenol-S-diglycidyl ether, epoxy resins having two or more epoxy groups in the molecule, and the like.

作為異氰酸酯系交聯劑,可列舉:1,2-伸乙基二異氰酸酯、1,4-伸丁基二異氰酸酯、1,6-六亞甲基二異氰酸酯等低級脂肪族聚異氰酸酯化合物;伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛爾酮二異氰酸酯、氫化甲苯二異氰酸酯、氫化二甲苯二異氰酸酯等脂肪族聚異氰酸酯化合物;2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、苯二亞甲基二異氰酸酯等芳香族聚異氰酸酯化合物等。Examples of isocyanate-based crosslinking agents include lower aliphatic polyisocyanate compounds such as 1,2-ethylidene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; Aliphatic polyisocyanate compounds such as pentyl diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate; 2,4-toluene diisocyanate, 2,6-toluene diisocyanate , 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate and other aromatic polyisocyanate compounds.

交聯劑的使用量例如可相對於丙烯酸系聚合物100質量份而設為約0.01質量份~15質量份,較佳為設為0.1質量份~10質量份(例如,0.2質量份~2質量份)。於以所述使用量包含交聯劑的情況下,有可獲得顯示出良好的黏著性能的黏著劑的傾向。The usage-amount of a crosslinking agent can be set as about 0.01 mass part - 15 mass parts, for example with respect to 100 mass parts of acrylic polymers, Preferably it is 0.1 mass part - 10 mass parts (for example, 0.2 mass part - 2 mass parts share). In the case where the crosslinking agent is contained in the above usage amount, there is a tendency that an adhesive exhibiting good adhesive performance can be obtained.

丙烯酸系黏著劑視需要亦可包含各種添加劑。作為添加劑,可列舉:表面潤滑劑、調平劑、抗氧化劑、防腐劑、光穩定劑、紫外線吸收劑、聚合抑制劑、矽烷偶合劑等。The acrylic adhesive may contain various additives as necessary. Examples of additives include surface lubricants, leveling agents, antioxidants, preservatives, light stabilizers, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, and the like.

丙烯酸系黏著劑視需要亦可包含黏著性賦予樹脂。黏著性賦予樹脂的種類並無特別限制,可列舉:松香系黏著性賦予樹脂、萜烯系黏著性賦予樹脂、烴系黏著性賦予樹脂、環氧系黏著性賦予樹脂、聚醯胺系黏著性賦予樹脂、彈性體系黏著性賦予樹脂、酚系黏著性賦予樹脂、酮系黏著性賦予樹脂等。丙烯酸系黏著劑中所含的黏著性賦予樹脂可為單獨一種,亦可為兩種以上。The acrylic adhesive may also contain an adhesiveness imparting resin as needed. The type of tackifying resin is not particularly limited, and examples thereof include rosin-based tackifying resins, terpene-based tackifying resins, hydrocarbon-based tackifying resins, epoxy-based tackifying resins, and polyamide-based tackifying resins. Imparting resins, elastic-based adhesiveness-imparting resins, phenolic adhesiveness-imparting resins, ketone-based adhesiveness-imparting resins, etc. The tackiness-imparting resin contained in the acrylic adhesive may be one kind alone, or two or more kinds thereof.

作為松香系黏著性賦予樹脂,可列舉:膠松香、木松香、塔羅油(tall oil)松香等未改質松香(生松香);藉由氫化、歧化、聚合等將未改質松香改質而成的改質松香(氫化松香、歧化松香、聚合松香、經其他化學方式修飾的松香等);其他各種松香衍生物等。 作為松香衍生物,可列舉:藉由醇類將未改質松香或改質松香酯化而成者(松香酯);藉由不飽和脂肪酸將未改質松香或改質松香改質而成者(不飽和脂肪酸改質松香);藉由不飽和脂肪酸將松香酯改質而成者(不飽和脂肪酸改質松香酯);對未改質松香、改質松香、不飽和脂肪酸改質松香或不飽和脂肪酸改質松香酯中的羧基進行還原處理而成者(松香醇);未改質松香、改質松香及所述松香衍生物(特別是松香酯)的金屬鹽;藉由以酸觸媒而於未改質松香、改質松香及所述松香衍生物上加成苯酚並進行熱聚合而獲得的松香苯酚樹脂等。Examples of rosin-based tackifying resins include unmodified rosins (raw rosins) such as gum rosin, wood rosin, and tall oil rosin; unmodified rosins modified by hydrogenation, disproportionation, polymerization, etc. Modified rosin (hydrogenated rosin, disproportionated rosin, polymerized rosin, rosin modified by other chemical methods, etc.); other various rosin derivatives, etc. Examples of rosin derivatives include those obtained by esterifying unmodified rosin or modified rosin with alcohols (rosin ester); those obtained by modifying unmodified rosin or modified rosin with unsaturated fatty acids (unsaturated fatty acid modified rosin); modified rosin ester by unsaturated fatty acid (unsaturated fatty acid modified rosin ester); unmodified rosin, modified rosin, unsaturated fatty acid modified rosin or unmodified rosin Carboxyl groups in modified rosin esters modified by saturated fatty acids are reduced (abietin alcohol); unmodified rosin, modified rosin and metal salts of the rosin derivatives (especially rosin esters); by using acid catalysts Rosin phenol resins obtained by adding phenol to unmodified rosin, modified rosin, and the rosin derivatives and thermally polymerizing them.

作為萜烯系黏著性賦予樹脂,可列舉:α-蒎烯聚合體、β-蒎烯聚合體、二戊烯聚合體等萜烯系樹脂;對該些萜烯系樹脂改質(酚改質、芳香族改質、氫化改質、烴改質等)而成的改質萜烯系樹脂等。作為改質萜烯系樹脂,可列舉:萜烯-酚系樹脂、苯乙烯改質萜烯系樹脂、芳香族改質萜烯系樹脂、氫化萜烯系樹脂等。Examples of terpene-based adhesiveness-imparting resins include terpene-based resins such as α-pinene polymers, β-pinene polymers, and dipentene polymers; modification of these terpene-based resins (phenol-modified , aromatic modification, hydrogenation modification, hydrocarbon modification, etc.) modified terpene-based resins, etc. Examples of the modified terpene-based resin include terpene-phenol-based resins, styrene-modified terpene-based resins, aromatic-modified terpene-based resins, hydrogenated terpene-based resins, and the like.

作為烴系黏著性賦予樹脂,可列舉:脂肪族系烴樹脂、芳香族系烴樹脂、脂肪族系環狀烴樹脂、脂肪族・芳香族系石油樹脂(苯乙烯-烯烴系共聚物等)、脂肪族・脂環族系石油樹脂、氫化烴樹脂、香豆酮系樹脂、香豆酮-茚系樹脂等。 作為脂肪族系烴樹脂,可列舉選自碳數為4~5左右的烯烴及二烯中的一種或兩種以上的脂肪族烴的聚合體等。作為烯烴,可列舉:1-丁烯、異丁烯、1-戊烯等。作為二烯,可列舉:丁二烯、1,3-戊二烯、異戊二烯等。Examples of hydrocarbon-based tackifying resins include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic and aromatic petroleum resins (styrene-olefin copolymers, etc.), Aliphatic and cycloaliphatic petroleum resins, hydrogenated hydrocarbon resins, coumarone-based resins, coumarone-indene-based resins, etc. Examples of the aliphatic hydrocarbon resin include polymers of one or more aliphatic hydrocarbons selected from olefins and dienes having about 4 to 5 carbon atoms. Examples of olefins include 1-butene, isobutene, 1-pentene and the like. As dienes, butadiene, 1,3-pentadiene, isoprene, etc. are mentioned.

作為芳香族系烴樹脂的例子,可列舉碳原子數8~10左右的含乙烯基的芳香族系烴(苯乙烯、乙烯基甲苯、α-甲基苯乙烯、茚、甲基茚等)的聚合體等。Examples of aromatic hydrocarbon resins include vinyl group-containing aromatic hydrocarbons (styrene, vinyltoluene, α-methylstyrene, indene, methylindene, etc.) with about 8 to 10 carbon atoms. aggregates etc.

作為脂肪族系環狀烴樹脂,可列舉:將所謂的「C4石油餾分」或「C5石油餾分」環化二聚體化後並進行聚合而成的脂環式烴系樹脂;環狀二烯化合物(環戊二烯、二環戊二烯、亞乙基降冰片烷、二戊烯等)的聚合體或其氫化物;對芳香族系烴樹脂或脂肪族・芳香族系石油樹脂的芳香環進行氫化而成的脂環式烴系樹脂等。Examples of aliphatic cyclic hydrocarbon resins include alicyclic hydrocarbon resins obtained by cyclodimerizing so-called "C4 petroleum fractions" or "C5 petroleum fractions" and polymerizing them; cyclic dienes Compounds (cyclopentadiene, dicyclopentadiene, ethylidene norbornane, dipentene, etc.) Alicyclic hydrocarbon resins obtained by hydrogenating rings, etc.

黏著性賦予樹脂較佳為軟化點(軟化溫度)為80℃以上(較佳為100℃以上)。藉由使用此種黏著性賦予樹脂,有可獲得更高性能的(例如,接著性高的)黏著劑的傾向。黏著性賦予樹脂的軟化點的上限並無特別限制,例如可設為200℃以下(較佳為180℃以下)。此外,將此處所謂的黏著性賦予樹脂的軟化點設為藉由日本工業標準(Japanese Industrial Standards,JIS)K 5902:2006及JIS K 2207:2006的任一者所規定的軟化點試驗方法(環球法)而測定的值。The tackiness-imparting resin preferably has a softening point (softening temperature) of 80° C. or higher (preferably 100° C. or higher). There is a tendency that an adhesive with higher performance (for example, high adhesiveness) can be obtained by using such an adhesiveness-imparting resin. The upper limit of the softening point of the tackiness-imparting resin is not particularly limited, and may be, for example, 200° C. or lower (preferably 180° C. or lower). In addition, the softening point of the tackiness-imparting resin referred to here is defined as the softening point test method specified by any one of Japanese Industrial Standards (Japanese Industrial Standards, JIS) K 5902: 2006 and JIS K 2207: 2006 ( The value determined by the ring and ball method.

黏著性賦予樹脂的使用量並無特別限制,可根據設為目標的黏著性能(接著力等)而適宜設定。例如,較佳為以固體成分基準計,相對於丙烯酸系聚合物100質量份,以10質量份~100質量份(較佳為15質量份~80質量份,更佳為20質量份~60質量份)的比例使用黏著性賦予樹脂。The usage-amount of tackiness imparting resin is not specifically limited, It can set suitably according to the tackiness performance (adhesive force etc.) aimed at. For example, it is preferable to use 10 to 100 parts by mass (preferably 15 to 80 parts by mass, more preferably 20 to 60 parts by mass) based on solid content relative to 100 parts by mass of the acrylic polymer. parts) using the tack-imparting resin.

(3)橡膠系黏著劑 本說明書中橡膠系黏著劑是指將橡膠系聚合物設為基礎聚合物的黏著劑。橡膠系聚合物並無特別限制,可為天然橡膠系聚合物(包含改質天然橡膠系聚合物),亦可為合成橡膠系聚合物。作為合成橡膠系聚合物,可列舉ABA型或AB型嵌段共聚物(A表示熱塑性嵌段,B表示橡膠嵌段。可列舉苯乙烯-異戊二烯-苯乙烯共聚物(Styrene-Isoprene-Styrene,SIS)、苯乙烯-丁二烯-苯乙烯共聚物(Styrene-Butadiene-Styrene,SBS)等)。橡膠系聚合物亦可為天然橡膠系聚合物與合成橡膠系聚合物的組合。(3) Rubber-based adhesive The rubber-based adhesive used in this specification refers to an adhesive in which a rubber-based polymer is used as a base polymer. The rubber-based polymer is not particularly limited, and may be a natural rubber-based polymer (including a modified natural rubber-based polymer) or a synthetic rubber-based polymer. Examples of synthetic rubber-based polymers include ABA-type or AB-type block copolymers (A represents a thermoplastic block, B represents a rubber block. Styrene-isoprene-styrene copolymer (Styrene-Isoprene- Styrene, SIS), styrene-butadiene-styrene copolymer (Styrene-Butadiene-Styrene, SBS) etc.). The rubber-based polymer may be a combination of a natural rubber-based polymer and a synthetic rubber-based polymer.

於橡膠系黏著劑包含合成橡膠系聚合物的情況下,作為合成橡膠系聚合物,可列舉:聚丁二烯、聚異戊二烯、丁基橡膠、聚異丁烯、苯乙烯丁二烯橡膠(Styrene Butadiene Rubber,SBR)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(Styrene-Ethylene-Butylene-Styrene,SEBS)、苯乙烯-異戊二烯-苯乙烯嵌段共聚物(SIS)等。When the rubber-based adhesive contains a synthetic rubber-based polymer, examples of the synthetic rubber-based polymer include polybutadiene, polyisoprene, butyl rubber, polyisobutylene, styrene butadiene rubber ( Styrene Butadiene Rubber, SBR), Styrene-Butadiene-Styrene Block Copolymer (SBS), Styrene-Ethylene-Butylene-Styrene Block Copolymer (Styrene-Ethylene-Butylene-Styrene, SEBS), Styrene-isoprene-styrene block copolymer (SIS), etc.

於橡膠系黏著劑包含改質天然橡膠系聚合物的情況下,改質天然橡膠系聚合物較佳為其50質量%以上(例如60質量%以上)為源自天然橡膠的結構部分者。作為改質天然橡膠系聚合物,可列舉使其他單體接枝於天然橡膠系聚合物而成的接枝改質天然橡膠系聚合物等。作為接枝於天然橡膠系聚合物的單體,可列舉丙烯酸系單體(具有丙烯醯基或甲基丙烯醯基的單體)、苯乙烯等。接枝於天然橡膠系聚合物的單體可為單獨一種,亦可為兩種以上。When the rubber-based adhesive contains a modified natural rubber-based polymer, the modified natural rubber-based polymer is preferably 50% by mass or more (for example, 60% by mass or more) of structural moieties derived from natural rubber. Examples of the modified natural rubber-based polymer include graft-modified natural rubber-based polymers obtained by grafting other monomers onto the natural rubber-based polymer, and the like. Examples of the monomer grafted onto the natural rubber-based polymer include acrylic monomers (monomers having an acryl group or a methacryl group), styrene, and the like. The monomer to be grafted to the natural rubber-based polymer may be one kind alone, or two or more kinds thereof.

作為接枝於天然橡膠系聚合物的丙烯酸系單體,可列舉:丙烯酸烷基酯(例如,丙烯酸甲酯、丙烯酸乙酯、丙烯酸異丙酯、丙烯酸第三丁酯等烷基的碳原子數為1~16的丙烯酸烷基酯)、甲基丙烯酸烷基酯(例如,甲基丙烯酸甲酯(Methyl methacrylate,MMA)、甲基丙烯酸乙酯、甲基丙烯酸異丙酯、甲基丙烯酸第三丁酯等烷基的碳原子數為1~16的甲基丙烯酸烷基酯)、丙烯酸、甲基丙烯酸等。 改質天然橡膠系聚合物較佳為接枝於天然橡膠系聚合物的單體中的50質量%以上為丙烯酸系單體者(丙烯酸改質天然橡膠系聚合物)。Examples of acrylic monomers grafted onto natural rubber-based polymers include alkyl acrylates (for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, tertiary butyl acrylate, etc. 1 to 16 alkyl acrylate), alkyl methacrylate (for example, methyl methacrylate (MMA), ethyl methacrylate, isopropyl methacrylate, third methacrylate C1-C16 alkyl methacrylates such as butyl esters), acrylic acid, methacrylic acid, and the like. The modified natural rubber-based polymer is preferably one in which 50% by mass or more of monomers grafted to the natural rubber-based polymer are acrylic monomers (acrylic acid-modified natural rubber-based polymer).

於橡膠系黏著劑的基礎聚合物為天然橡膠系聚合物的情況下,天然橡膠系聚合物例如較佳為MS(1+4)100℃(使用L型轉子、預熱1分鐘、黏度測定時間為4分鐘、試驗溫度為100℃)的測定條件下的門尼黏度為10~60左右者。 於其他一態樣中,較佳為甲基丙烯酸甲酯(MMA)接枝於天然橡膠系聚合物而成的丙烯酸改質天然橡膠系聚合物(NR-MMA接枝共聚物)。所述接枝共聚物可藉由常法而製造,亦可作為市售品而獲取。NR-MMA接枝共聚物中的MMA的接枝率(由鍵結於天然橡膠的MMA的質量/用於接枝化的天然橡膠的質量´100(%)而表示,通常與根據用於NR-MMA接枝共聚物的製造的天然橡膠和MMA的質量比而算出的值同等)例如可設為1%~120%,較佳為5%~100%,更佳為10%~90%,進而佳為30%~80%。接枝化率較佳為50%~90%,更佳為60%~80%。若接枝化率為1%以上,則可抑制黏著力變得過高,若接枝化率為120%以下,則可抑制相對於SUS板等黏附體的黏著力變得過低。可將用於NR-MMA接枝共聚物的製造的MMA的一部分(例如,接枝於天然橡膠的單體整體的5質量%以下,典型而言為3質量%以下)置換為其他單體。In the case where the base polymer of the rubber-based adhesive is a natural rubber-based polymer, for example, the natural rubber-based polymer is preferably MS (1+4) 100°C (use an L-shaped rotor, preheat for 1 minute, and measure the viscosity The Mooney viscosity is about 10 to 60 under the measurement conditions of 4 minutes and a test temperature of 100°C. In another aspect, an acrylic-modified natural rubber-based polymer (NR-MMA graft copolymer) obtained by grafting methyl methacrylate (MMA) to a natural rubber-based polymer is preferred. The said graft copolymer can be manufactured by a normal method, and can also acquire it as a commercial item. The graft ratio of MMA in the NR-MMA graft copolymer (expressed by the mass of MMA bonded to natural rubber/the mass of natural rubber used for grafting ´100 (%) is usually the same as that used for NR -The mass ratio of the natural rubber and MMA produced by the MMA graft copolymer is equal to the calculated value) For example, it can be set to 1% to 120%, preferably 5% to 100%, more preferably 10% to 90%, More preferably, it is 30% to 80%. The grafting rate is preferably from 50% to 90%, more preferably from 60% to 80%. When the grafting rate is 1% or more, the adhesive force can be suppressed from becoming too high, and when the grafting rate is 120% or less, the adhesive force to adherends such as SUS plates can be prevented from becoming too low. A part of MMA used in the production of the NR-MMA graft copolymer (for example, 5% by mass or less, typically 3% by mass or less of the monomers grafted to natural rubber) may be substituted with other monomers.

橡膠系黏著劑除基礎聚合物以外亦可包含其他聚合物(以下,亦稱為副聚合物)。作為副聚合物,可列舉:可成為公知的丙烯酸系黏著劑、聚酯系黏著劑、聚胺基甲酸酯系黏著劑、矽酮系黏著劑等的基礎聚合物的丙烯酸系聚合物、聚酯系聚合物、聚胺基甲酸酯系聚合物、矽酮聚合物等。或者亦可為所述橡膠系聚合物中的基礎聚合物以外者。橡膠系黏著劑中所含的副聚合物可為單獨一種,亦可為兩種以上。作為基礎聚合物與副聚合物的組合,可列舉:作為基礎聚合物的天然橡膠系聚合物與作為副聚合物的NR-MMA接枝共聚物的組合、作為基礎聚合物的NR-MMA接枝共聚物與作為副聚合物的天然橡膠系聚合物的組合等。The rubber-based adhesive may contain other polymers (hereinafter also referred to as subpolymers) in addition to the base polymer. Examples of subpolymers include acrylic polymers, polyacrylic polymers that can be used as base polymers of known acrylic adhesives, polyester adhesives, polyurethane adhesives, silicone adhesives, etc. Ester polymers, polyurethane polymers, silicone polymers, etc. Or it may be other than the base polymer in the said rubber-type polymer. The subpolymer contained in the rubber-based adhesive may be a single type or two or more types. Examples of the combination of the base polymer and the subpolymer include a combination of a natural rubber polymer as the base polymer and an NR-MMA graft copolymer as the subpolymer, and a NR-MMA graft copolymer as the base polymer. A combination of a copolymer and a natural rubber-based polymer as a subpolymer, etc.

於橡膠系黏著劑包含基礎聚合物與副聚合物的情況下,可相對於基礎聚合物100質量份而以100質量份以下的使用量(於副聚合物為兩種以上的情況下,為其合計)使用副聚合物。通常適當的是將相對於基礎聚合物100質量份而言的副聚合物的使用量設為70質量份以下,較佳為設為50質量份以下。橡膠系黏著劑亦可實質上不包含副聚合物(即,聚合物成分實質上100質量%為基礎聚合物)。另外,亦可為實質上不含有橡膠系聚合物以外的聚合物成分的橡膠系黏著劑(例如,實質上不含有天然橡膠及改質天然橡膠以外的聚合物成分的橡膠系黏著劑)。When the rubber-based adhesive contains a base polymer and a subpolymer, it can be used in an amount of 100 parts by mass or less relative to 100 parts by mass of the base polymer (in the case of two or more subpolymers, the total) using subpolymers. Usually, it is appropriate to make the usage-amount of the subpolymer 70 mass parts or less with respect to 100 mass parts of base polymers, Preferably it is 50 mass parts or less. The rubber-based adhesive may not substantially contain a subpolymer (that is, substantially 100% by mass of the polymer component is the base polymer). In addition, a rubber-based adhesive that does not substantially contain polymer components other than rubber-based polymers (for example, a rubber-based adhesive that does not substantially contain polymer components other than natural rubber and modified natural rubber) may be used.

橡膠系黏著劑除聚合物成分以外亦可包含黏著性賦予劑。特別是於包含其自身的黏著性低的天然橡膠系聚合物作為聚合物成分的情況下,藉由包含黏著性賦予劑,能夠相對於多種黏附體而顯示出高的黏著性。於橡膠系黏著劑包含黏著性賦予劑的情況下,作為黏著性賦予劑,例如可列舉作為丙烯酸系黏著劑中可包含的黏著性賦予樹脂而例示者。The rubber-based adhesive may contain an adhesiveness imparting agent in addition to the polymer component. In particular, when a natural rubber-based polymer with low adhesiveness itself is included as a polymer component, by including an adhesiveness-imparting agent, it is possible to exhibit high adhesiveness to various adherends. When the rubber-based adhesive contains the tackiness-imparting agent, examples of the tackiness-imparting agent include those exemplified as the tackiness-imparting resin that may be contained in the acrylic adhesive.

於橡膠系黏著劑包含聚合物成分與黏著性賦予劑的情況下,例如相對於聚合物成分100質量份,可將黏著性賦予劑的使用量(於黏著性賦予劑為兩種以上的情況下,為其合計)設為20質量份~150質量份(較佳為30質量份~100質量份)。若黏著性賦予劑的使用量為20質量份以上,則有可充分地獲得相對於引線框架等黏附體的黏著力的傾向。另一方面,若黏著性賦予劑的使用量為150質量份以下,則有可充分地獲得相對於引線框架等黏附體的黏著力(特別是低溫環境下的黏著力)的傾向。In the case where the rubber-based adhesive includes a polymer component and an adhesiveness-imparting agent, for example, the amount of the adhesiveness-imparting agent (in the case of two or more types of adhesiveness-imparting agents) can be adjusted relative to 100 parts by mass of the polymer component. , and the total thereof) shall be 20 to 150 parts by mass (preferably 30 to 100 parts by mass). When the usage-amount of an adhesiveness imparting agent is 20 mass parts or more, the adhesive force with respect to adherends, such as a lead frame, exists in the tendency for sufficient acquisition. On the other hand, when the usage-amount of the tackiness imparting agent is 150 mass parts or less, the adhesive force (particularly the adhesive force in a low-temperature environment) with respect to the adherend, such as a lead frame, tends to be fully acquired.

將橡膠系黏著劑賦予至基材上的方法並無特別限制。例如可適宜採用:藉由將使成為橡膠系黏著劑的成分溶解或分散於適當的介質中而成的黏著劑組成物塗附於基材並使其乾燥而直接於基材上形成黏著劑層的方法、將形成於具有剝離性的表面上的黏著劑層轉印至基材的方法等公知的方法。黏著劑組成物例如可藉由常法將聚合物成分、典型而言黏著性賦予劑、視需要使用的其他成分、以及所述介質混合而製備。The method of applying the rubber-based adhesive to the substrate is not particularly limited. For example, an adhesive composition obtained by dissolving or dispersing the components to be a rubber-based adhesive in an appropriate medium is applied to the base material and dried to form an adhesive layer directly on the base material, preferably. known methods such as a method of transferring an adhesive layer formed on a peelable surface to a substrate. The adhesive composition can be prepared, for example, by conventionally mixing a polymer component, typically an adhesive agent, other components used as necessary, and the medium.

橡膠系黏著劑視需要亦可包含硫化促進劑。作為硫化促進劑,可使用二硫胺甲酸類(二甲基二硫胺甲酸鈉、二乙基二硫胺甲酸鈉、二甲基二硫胺甲酸鋅、二乙基二硫胺甲酸鋅等)、噻唑類(2-巰基苯并噻唑、二苯并噻唑基二硫醚等)、胍類(二苯基胍、二-鄰甲苯基胍等)、次磺醯胺類(苯并噻唑基-2-二乙基次磺醯胺、N-環己基-2-苯并噻唑基次磺醯胺等)、秋蘭姆類(一硫化四甲基秋蘭姆、二硫化四甲基秋蘭姆等)、黃原酸類(異丙基黃原酸鈉、異丙基黃原酸鋅等)、醛氨類(乙醛氨、六亞甲基四胺等)、醛胺類(正丁基醛苯胺、丁基醛單丁基胺等)、硫脲類(二乙基硫脲、三甲基硫脲等)等。橡膠系黏著劑中所含的硫化促進劑可為單獨一種,亦可為兩種以上。例如,亦可併用二硫胺甲酸類與秋蘭姆類。例如相對於聚合物成分100質量份,可將硫化促進劑的使用量設為0.1質量份~10質量份(較佳為0.5質量份~5質量份)。The rubber-based adhesive may also contain a vulcanization accelerator as necessary. As the vulcanization accelerator, dithiocarbamic acids (sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, etc.), thiazole Classes (2-mercaptobenzothiazole, dibenzothiazolyl disulfide, etc.), guanidines (diphenylguanidine, di-o-tolylguanidine, etc.), sulfenamides (benzothiazolyl-2- Diethylsulfenamide, N-cyclohexyl-2-benzothiazolylsulfenamide, etc.), thiurams (tetramethylthiuram monosulfide, tetramethylthiuram disulfide, etc.) , xanthic acids (sodium isopropyl xanthate, zinc isopropyl xanthate, etc.), aldehydes and ammonia (acetaldehyde ammonia, hexamethylenetetramine, etc.), aldehydes and amines (n-butyl aldehyde aniline, butyl aldehyde monobutylamine, etc.), thioureas (diethylthiourea, trimethylthiourea, etc.), etc. The vulcanization accelerator contained in the rubber-based adhesive may be a single type or two or more types. For example, dithiocarbamic acids and thiurams may be used in combination. For example, the vulcanization accelerator may be used in an amount of 0.1 to 10 parts by mass (preferably 0.5 to 5 parts by mass) relative to 100 parts by mass of the polymer component.

橡膠系黏著劑視需要亦可包含交聯劑。作為交聯劑,可列舉:異氰酸酯化合物、硫、含硫化合物、酚樹脂、有機金屬化合物等。交聯劑較佳為異氰酸酯化合物,更佳為二官能以上的異氰酸酯化合物。作為二官能以上的異氰酸酯化合物,可列舉:伸丁基二異氰酸酯、六亞甲基二異氰酸酯等低級脂肪族聚異氰酸酯類;伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛爾酮二異氰酸酯等脂環族異氰酸酯類;2,4-甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、苯二亞甲基二異氰酸酯等芳香族二異氰酸酯類;三羥甲基丙烷/甲苯二異氰酸酯三聚體加成物(日本聚胺酯工業股份有限公司製造,商品名「克羅奈特(Coronate)L」)、三羥甲基丙烷/六亞甲基二異氰酸酯三聚體加成物(日本聚胺酯工業股份有限公司製造,商品名「克羅奈特(Coronate)HL」)、六亞甲基二異氰酸酯的異氰脲酸酯體(日本聚胺酯工業股份有限公司製造,商品名「克羅奈特(Coronate)HX」)等異氰酸酯加成物等。橡膠系黏著劑中所含的交聯劑可為單獨一種,亦可為兩種以上。相對於聚合物成分100質量份,較佳為將交聯劑的使用量(異氰酸酯化合物的情況)設為0.3質量份~10質量份(例如0.5質量份~5質量份)。The rubber-based adhesive may also contain a crosslinking agent as necessary. Examples of the crosslinking agent include isocyanate compounds, sulfur, sulfur-containing compounds, phenol resins, organometallic compounds, and the like. The crosslinking agent is preferably an isocyanate compound, more preferably a difunctional or higher isocyanate compound. Examples of isocyanate compounds having more than two functions include: lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate Cycloaliphatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate and other aromatic diisocyanates; trimethylolpropane/toluene diisocyanate Trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate) L"), trimethylolpropane/hexamethylene diisocyanate trimer adduct (Nippon Polyurethane Industrial Co., Ltd., trade name "Coronate (Coronate) HL"), isocyanurate body of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate (Coronate) HL") Coronate) HX") and other isocyanate adducts, etc. The crosslinking agent contained in the rubber-based adhesive may be a single type or two or more types. It is preferable to set the usage-amount (in the case of an isocyanate compound) of a crosslinking agent to 0.3-10 mass parts (for example, 0.5-5 mass parts) with respect to 100 mass parts of polymer components.

橡膠系黏著劑視需要亦可包含硫化促進助劑。作為硫化促進助劑,可列舉硬脂酸鋅等。藉由使用硫化促進助劑,可使硫化促進劑活性化而促進硫化效率。於包含硫化促進助劑的情況下,例如相對於聚合物成分100質量份,可將其使用量設為0.1質量份~10質量份(較佳為0.5質量份~5質量份)。The rubber-based adhesive may also contain a vulcanization accelerator as necessary. Zinc stearate etc. are mentioned as a vulcanization acceleration auxiliary agent. By using a vulcanization accelerator, the vulcanization accelerator can be activated to increase vulcanization efficiency. When the vulcanization accelerator is included, for example, the amount used may be 0.1 to 10 parts by mass (preferably 0.5 to 5 parts by mass) relative to 100 parts by mass of the polymer component.

橡膠系黏著劑視需要亦可包含添加劑。作為添加劑,可列舉:軟化劑、阻燃劑、抗靜電劑、光穩定劑(自由基捕捉劑、紫外線吸收劑等)、抗氧化劑等。The rubber-based adhesive may contain additives as necessary. Examples of additives include softeners, flame retardants, antistatic agents, light stabilizers (radical scavengers, ultraviolet absorbers, etc.), antioxidants, and the like.

(4)胺基甲酸酯系黏著劑 本說明書中胺基甲酸酯系黏著劑是指將胺基甲酸酯聚合物設為基礎聚合物的黏著劑。作為胺基甲酸酯聚合物,可列舉使多元醇與聚異氰酸酯化合物反應而獲得的聚合物,較佳為使多元醇與過量的聚異氰酸酯化合物反應而獲得的含末端異氰酸酯基的胺基甲酸酯預聚物(以下,稱為「末端NCO預聚物」)。末端NCO預聚物可藉由使各種多元醇與過量的聚異氰酸酯化合物例如以OH與NCO的當量比(OH的個數/NCO的個數)為1/1.2~3.5的方式反應而合成。反應根據需要可於適當的反應觸媒(二丁基錫二月桂酸酯等有機錫系觸媒、辛酸鉍等鉍系觸媒、1,4-二氮雜[2.2.2]雙環辛烷等三級胺系觸媒等)的存在下,例如以20℃~90℃(較佳為60℃~90℃)且1小時~7小時的條件進行。(4) Urethane-Based Adhesive The urethane-based adhesive used in this specification refers to an adhesive in which a urethane polymer is used as a base polymer. Examples of the urethane polymer include polymers obtained by reacting polyols with polyisocyanate compounds, preferably terminal isocyanate group-containing urethanes obtained by reacting polyols with excess polyisocyanate compounds. Ester prepolymer (hereinafter referred to as "terminated NCO prepolymer"). The terminal NCO prepolymer can be synthesized by reacting various polyols with excess polyisocyanate compound such that the equivalent ratio of OH to NCO (number of OH/number of NCO) is 1/1.2 to 3.5. The reaction can be carried out with appropriate reaction catalysts (organic tin catalysts such as dibutyltin dilaurate, bismuth catalysts such as bismuth octoate, tertiary catalysts such as 1,4-diaza[2.2.2]bicyclooctane, etc. amine-based catalyst, etc.), for example, at 20° C. to 90° C. (preferably 60° C. to 90° C.) and 1 hour to 7 hours.

就預聚物的儲藏穩定性及硬化物的柔軟性的觀點而言,末端NCO預聚物中的末端異氰酸酯基(NCO)的含量較佳為0.2質量%~15.0質量%,更佳為0.5質量%~3.5質量%。末端NCO預聚物的數量平均分子量通常為3,000~50,000,就操作的觀點而言,較佳為4,000~30,000。From the viewpoint of the storage stability of the prepolymer and the flexibility of the cured product, the content of the terminal isocyanate group (NCO) in the terminal NCO prepolymer is preferably 0.2 mass % to 15.0 mass %, more preferably 0.5 mass % % to 3.5% by mass. The number average molecular weight of the terminal NCO prepolymer is usually 3,000 to 50,000, preferably 4,000 to 30,000 from the viewpoint of handling.

作為多元醇(polyol),可列舉:使環氧丙烷或環氧丙烷與環氧乙烷等環氧烷、與乙二醇、丙二醇、甘油、三羥甲基丙烷、季戊四醇、山梨糖醇、蔗糖等多元醇(polyhydric alcohol)進行加成聚合而成的聚醚多元醇類;乙二醇、丙二醇及該些的寡聚二醇類;丁二醇、己二醇、及聚四亞甲基醚二醇;聚己內酯多元醇;聚乙二醇己二酸酯等聚酯多元醇類;聚丁二烯多元醇類;蓖麻油等具有羥基的高級脂肪酸酯類;使乙烯單體與聚醚多元醇類或聚酯多元醇類進行接枝化而成的聚合物多元醇類等。用於胺基甲酸酯聚合物的合成的多元醇可為單獨一種,亦可為兩種以上。Examples of polyols include propylene oxide or propylene oxide and alkylene oxides such as ethylene oxide, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, etc. Polyether polyols formed by addition polymerization of polyhydric alcohols; ethylene glycol, propylene glycol and their oligomeric glycols; butylene glycol, hexylene glycol, and polytetramethylene ether Diols; polycaprolactone polyols; polyester polyols such as polyethylene glycol adipate; polybutadiene polyols; high-level fatty acid esters with hydroxyl groups such as castor oil; Polymer polyols obtained by grafting ether polyols or polyester polyols, etc. The polyhydric alcohol used for the synthesis|combination of a urethane polymer may be single 1 type, and may be 2 or more types.

多元醇亦可為聚合物。於多元醇為聚合物的情況下,就反應性、作業性的觀點而言,其數量平均分子量較佳為500~20,000,更佳為1,000~20,000。 就抑制發泡、作業性、硬化性及物性的穩定性的觀點而言,尤其就於與後述特定的硬化觸媒組合時獲得該些特性的優異的平衡的觀點而言,多元醇較佳為作為環氧丙烷的加成物的聚氧伸烷基多元醇,或作為環氧丙烷與環氧乙烷的加成物的聚氧伸烷基多元醇。就實用性的觀點而言,更佳為作為環氧丙烷的加成物的聚氧伸烷基多元醇(即聚伸丙基多元醇),進而佳為聚丙二醇。Polyols can also be polymers. When the polyol is a polymer, its number average molecular weight is preferably from 500 to 20,000, more preferably from 1,000 to 20,000, from the viewpoint of reactivity and workability. From the viewpoint of suppressing foaming, workability, curability and stability of physical properties, especially from the viewpoint of obtaining an excellent balance of these properties when combined with a specific curing catalyst described later, the polyol is preferably Polyoxyalkylene polyols as adducts of propylene oxide, or polyoxyalkylene polyols as adducts of propylene oxide and ethylene oxide. From a practical point of view, polyoxyalkylene polyol (that is, polypropylene glycol) which is an adduct of propylene oxide is more preferable, and polypropylene glycol is still more preferable.

多元醇亦可為松香二醇。藉由使用松香二醇,成為黏著劑的黏著力更優異者。松香二醇為於分子內分別具有兩個松香骨架與羥基的二醇。 作為松香二醇,可列舉:使松香與多元醇反應而獲得的松香酯、松香與雙酚A二縮水甘油醚等的反應物等。該些松香二醇可藉由先前已知的方法來製造。 於松香二醇中,就與NCO末端預聚物的相容性的觀點而言,較佳為具有聚氧伸烷基骨架者。作為具有聚氧伸烷基骨架的松香二醇的市售品,可列舉:派因克里斯特(Pinecrystal)D-6011、KE-615-3、D-6250(均為荒川化學工業股份有限公司)等。The polyol may also be rosin diol. By using rosin diol, the adhesive force of the adhesive becomes more excellent. Rosin diol is a diol having two rosin skeletons and a hydroxyl group in the molecule. Examples of the rosin diol include rosin esters obtained by reacting rosin with polyhydric alcohols, reaction products of rosin and bisphenol A diglycidyl ether, and the like. These rosin diols can be produced by a previously known method. Among rosin diols, those having a polyoxyalkylene skeleton are preferred from the viewpoint of compatibility with NCO-terminated prepolymers. Examples of commercially available rosin diols having a polyoxyalkylene skeleton include Pinecrystal D-6011, KE-615-3, and D-6250 (all of which are Arakawa Chemical Co., Ltd. )Wait.

松香二醇較佳為與其他多元醇併用。其他多元醇較佳為聚丙二醇。於併用松香二醇與其他多元醇的情況下,就硬化後的性狀的觀點而言,松香二醇的使用量較佳為多元醇總量的50質量%以下,更佳為2質量%~30質量%,進而佳為3質量%~15質量%。Rosin diol is preferably used in combination with other polyols. The other polyol is preferably polypropylene glycol. When using rosin diol and other polyols in combination, the amount of rosin diol used is preferably 50% by mass or less of the total amount of polyols, more preferably 2% by mass to 30% by mass, from the viewpoint of properties after hardening. % by mass, more preferably 3% by mass to 15% by mass.

多元醇亦可為多官能多元醇。例如,藉由使用四官能以上(較佳為四官能~八官能)的多官能多元醇,成為黏著劑的硬化後的黏著力(黏著強度(peel strength))更優異者。The polyols can also be polyfunctional polyols. For example, by using a tetrafunctional or higher (preferably tetrafunctional to octafunctional) polyfunctional polyol, the adhesive becomes more excellent in the adhesive force (peel strength) after curing of the adhesive.

作為多官能多元醇,可列舉:四醇(季戊四醇、二甘油等)、五醇(三甘油、半乳糖等)、六醇(二季戊四醇、山梨糖醇等)、七醇、八醇(三季戊四醇、蔗糖等)、於該些多官能多元醇上加成有環氧乙烷、環氧丙烷等而成者等。就通用性與效果的觀點而言,較佳為季戊四醇的烷氧化物加成物。該些多官能多元醇可藉由先前已知的方法來製造,亦可作為市售品而獲取。作為多官能多元醇的市售品,可列舉:EL-410NE(旭硝子股份有限公司)、POLYPL 4525(柏斯托精細化學品(Perstorp Specialty Chemicals AB)公司)等。Examples of polyfunctional polyols include tetraols (pentaerythritol, diglycerol, etc.), pentaols (triglycerol, galactose, etc.), hexaols (dipentaerythritol, sorbitol, etc.), heptaols, octals (tripentaerythritol, etc.) , sucrose, etc.), those obtained by adding ethylene oxide, propylene oxide, etc. to these polyfunctional polyols, etc. From the viewpoint of versatility and effect, an alkoxide adduct of pentaerythritol is preferable. These polyfunctional polyols can be produced by a conventionally known method, and can also be obtained as a commercial item. Examples of commercially available polyfunctional polyols include EL-410NE (Asahi Glass Co., Ltd.), POLYPL 4525 (Perstorp Specialty Chemicals AB), and the like.

多官能多元醇亦可為聚合物。於多官能多元醇為聚合物的情況下,其數量平均分子量通常為100~2,000,就性狀及反應性的觀點而言,較佳為300~700。Multifunctional polyols can also be polymers. When the polyfunctional polyol is a polymer, the number average molecular weight thereof is usually 100 to 2,000, and preferably 300 to 700 from the viewpoint of properties and reactivity.

多官能多元醇較佳為與其他多元醇併用。其他多元醇較佳為聚丙二醇,更佳為聚丙二醇與松香二醇的組合。於併用多官能多元醇與其他多元醇的情況下,就硬化物(黏著體)的柔軟性的觀點而言,多官能多元醇的使用量較佳為多官能多元醇的羥基的個數成為多元醇整體的羥基的個數的60%以下的量,更佳為成為5%~20%的量。 The polyfunctional polyol is preferably used in combination with other polyols. The other polyol is preferably polypropylene glycol, more preferably a combination of polypropylene glycol and rosin glycol. In the case of using a polyfunctional polyol in combination with other polyols, from the viewpoint of the flexibility of the cured product (adhesive), the amount of the polyfunctional polyol used is preferably such that the number of hydroxyl groups of the polyfunctional polyol becomes multiple The amount is 60% or less of the number of hydroxyl groups in the entire alcohol, more preferably 5% to 20%.

聚異氰酸酯化合物並無特別限制,亦可為從屬於芳香族、脂肪族或脂環族的任意者。具體而言,可列舉:甲苯二異氰酸酯(Toluene diisocyanate,TDI)、二苯基甲烷二異氰酸酯(Diphenyl methane diisocyanate,MDI)、3,3'-二甲基-4,4'-聯苯二異氰酸酯、1,4-苯二異氰酸酯、苯二亞甲基二異氰酸酯、四甲基苯二亞甲基二異氰酸酯、萘二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、粗(crude)TDI、聚亞甲基.聚苯基異氰酸酯、異佛爾酮二異氰酸酯(Isophorone diisocyanate,IPDI)、六亞甲基二異氰酸酯、氫化苯二亞甲基二異氰酸酯等。另外,亦可為該些聚異氰酸酯化合物的異氰脲酸酯化物、碳二醯亞胺化物、縮二脲化物等。用於胺基甲酸酯聚合物的合成的聚異氰酸酯化合物可為單獨一種,亦可為兩種以上。其中,就預聚物的性狀、硬化後的柔軟性、非黃變性及安全性的觀點而言,較佳為IPDI。 The polyisocyanate compound is not particularly limited, and may be any one belonging to aromatic, aliphatic, or alicyclic. Specifically, toluene diisocyanate (Toluene diisocyanate, TDI), diphenylmethane diisocyanate (Diphenylmethane diisocyanate, MDI), 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 1,4-phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, naphthalene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, crude TDI, Polymethylene. Polyphenylisocyanate, isophorone diisocyanate (IPDI), hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and the like. In addition, isocyanurate compounds, carbodiimide compounds, biuret compounds, etc. of these polyisocyanate compounds may be used. The polyisocyanate compound used for the synthesis|combination of a urethane polymer may be single 1 type, and may be 2 or more types. Among them, IPDI is preferred from the viewpoints of properties of the prepolymer, flexibility after curing, non-yellowing property, and safety.

聚異氰酸酯化合物較佳為包含三官能以上(較佳為三官能~六官能)的多官能聚異氰酸酯。藉由使用三官能以上的多官能聚異氰酸酯,成為黏著劑的硬化後的黏著力(黏著強度)更優異者。 作為多官能聚異氰酸酯的市售品,可列舉:克羅奈特(Coronate)HX(脂環族聚異氰酸酯,日本聚胺酯工業股份有限公司)、塔克奈特(Takenate)D-170N(脂環族聚異氰酸酯,武田藥品股份有限公司)、蘇米杜爾(Sumidur)N-3500(脂肪族聚異氰酸酯,住化拜耳胺酯股份有限公司)、蘇米杜爾(Sumidur)N-3200(脂肪族聚異氰酸酯,住化拜耳胺酯股份有限公司)、多耐德(Duranate)24A-100及多耐德(Duranate)E-405-80T(旭化成化學股份有限公司)等。The polyisocyanate compound is preferably a polyfunctional polyisocyanate containing more than trifunctional (preferably trifunctional to hexafunctional). By using the polyfunctional polyisocyanate of trifunctional or more, the adhesive force (adhesive strength) after hardening of an adhesive becomes more excellent. Commercially available polyfunctional polyisocyanates include: Coronate (Coronate) HX (alicyclic polyisocyanate, Nippon Polyurethane Industry Co., Ltd.), Takenate (Takenate) D-170N (alicyclic Polyisocyanate, Takeda Pharmaceutical Co., Ltd.), Sumidur (Sumidur) N-3500 (aliphatic polyisocyanate, Sumika Bayer Amide Co., Ltd.), Sumidur (Sumidur) N-3200 (aliphatic polyisocyanate Isocyanate, Sumika Bayer Amine Co., Ltd.), Duranate (Duranate) 24A-100 and Duranate (Duranate) E-405-80T (Asahi Kasei Chemical Co., Ltd.), etc.

多官能聚異氰酸酯化合物較佳為與其他聚異氰酸酯化合物併用。其他聚異氰酸酯化合物較佳為IPDI。於併用多官能聚異氰酸酯化合物與其他聚異氰酸酯化合物的情況下,就反應後的性狀的觀點而言,多官能聚異氰酸酯化合物的使用量較佳為多官能聚異氰酸酯化合物的NCO基的個數成為聚異氰酸酯化合物整體的NCO基的個數的60%以下的量,更佳為成為5%~20%的量。The polyfunctional polyisocyanate compound is preferably used in combination with other polyisocyanate compounds. The other polyisocyanate compound is preferably IPDI. In the case of using a polyfunctional polyisocyanate compound and another polyisocyanate compound in combination, from the viewpoint of properties after the reaction, the amount of the polyfunctional polyisocyanate compound used is preferably such that the number of NCO groups of the polyfunctional polyisocyanate compound becomes polyfunctional. The quantity is 60% or less of the number of objects of the NCO group of the whole isocyanate compound, More preferably, it is the quantity which becomes 5% - 20%.

末端NCO預聚物視需要可使多元醇、過量的聚異氰酸酯化合物、以及單醇反應而獲得。於該情況下,成為黏著劑的硬化後的黏著力(黏著強度)更優異者。The terminal NCO prepolymer can be obtained by reacting a polyol, an excess polyisocyanate compound, and a monoalcohol as needed. In this case, the adhesive agent becomes more excellent in the adhesive force (adhesive strength) after hardening.

作為單醇,可列舉:聚氧伸烷基系單醇、聚酯單醇、聚醚・酯單醇、高級飽和單醇、具有乙烯性不飽和雙鍵的單醇等。於使用單醇的情況下,可為單獨一種,亦可為兩種以上。Examples of monoalcohols include polyoxyalkylene monoalcohols, polyester monoalcohols, polyether/ester monoalcohols, higher saturated monoalcohols, monoalcohols having ethylenically unsaturated double bonds, and the like. When using monoalcohol, it may be single type, and may be two or more types.

作為聚氧伸烷基系單醇,可列舉將含有一個活性氫的烷基化合物等作為起始劑,使環氧乙烷、環氧丙烷、環氧丁烷、四氫呋喃等環氧烷開環加成聚合而成的於分子內含有一個羥基的高分子量的聚氧伸烷基系單醇等。 作為聚酯單醇,例如可列舉:由內酯系聚酯單醇、多元醇、與飽和脂肪酸或(甲基)丙烯酸、肉桂酸或碳數10以上的高級不飽和脂肪酸即油酸、亞麻油酸、次亞麻油酸等具有乙烯性不飽和雙鍵的羧酸而獲得的酯單醇等,所述內酯系聚酯單醇、多元醇是將已知的聚酯多元醇的末端羥基的烷基化改質物、單羥基化合物作為起始劑而使環狀內酯化合物進行開環加成共聚反應或酯化反應而獲得。 作為聚醚・酯單醇,可列舉使所述(單)環氧烷加成聚合於脂肪酸酯單醇而成的聚氧伸烷基脂肪酸酯單醇等。 作為高級飽和單醇,可列舉:月桂醇、肉豆蔻醇、鯨蠟醇、硬脂醇等碳數10以上的直鏈狀且一價的高級飽和醇等。 作為具有乙烯性不飽和雙鍵的單醇,可列舉:油醇、亞麻醇、次亞麻醇等碳數10以上的直鏈狀且一價的高級不飽和醇、烯丙基醇等。 其中,就通用及安全性的觀點而言,較佳為聚氧伸烷基系單醇,更佳為聚氧伸丙基烷基醚。 單醇亦可為聚合物。於單醇為聚合物的情況下,其數量平均分子量例如亦可為100~10,000,就通用性及操作的觀點而言,較佳為500~10,000。 作為聚合物的單醇的市售品可列舉PML-S1004F(旭硝子股份有限公司)等。 於使用作為聚合物的單醇的情況下,就硬化後的性能的觀點而言,相對於多元醇總量,單醇的使用量較佳為5質量%~50質量%,更佳為5質量%~30質量%。Examples of polyoxyalkylene-based monoalcohols include ring-opening and addition of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, using an alkyl compound containing one active hydrogen as an initiator. It is a polymerized high molecular weight polyoxyalkylene-based monoalcohol containing a hydroxyl group in the molecule. Examples of polyester monoalcohols include oleic acid, linseed oil, and saturated fatty acid or (meth)acrylic acid, cinnamic acid, or higher unsaturated fatty acid having 10 or more carbon atoms, such as lactone-based polyester monool or polyol. ester monoalcohol obtained from carboxylic acids having ethylenically unsaturated double bonds, such as linoleic acid and linoleic acid, etc., and the lactone-based polyester monool and polyol are obtained by combining the terminal hydroxyl groups of known polyester polyols It is obtained by subjecting a cyclic lactone compound to a ring-opening addition copolymerization reaction or an esterification reaction using an alkylated modified product and a monohydroxy compound as an initiator. Examples of the polyether/ester monool include polyoxyalkylene fatty acid ester monool obtained by addition-polymerizing the (mono)alkylene oxide to fatty acid ester monool, and the like. Examples of higher saturated monoalcohols include linear monovalent higher saturated alcohols having 10 or more carbon atoms such as lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol. Examples of the monoalcohol having an ethylenically unsaturated double bond include straight-chain monovalent higher unsaturated alcohols having 10 or more carbon atoms such as oleyl alcohol, linoleyl alcohol, and linoleyl alcohol, and allyl alcohol. Among these, polyoxyalkylene-based monoalcohols are preferable, and polyoxypropylene alkyl ethers are more preferable from the viewpoint of general use and safety. Monoalcohols can also be polymers. When the monoalcohol is a polymer, the number average molecular weight may be, for example, 100 to 10,000, and preferably 500 to 10,000 from the viewpoint of versatility and handling. As a commercial item of the monoalcohol of a polymer, PML-S1004F (Asahi Glass Co., Ltd.) etc. are mentioned. When using monoalcohol as a polymer, from the viewpoint of performance after curing, the amount of monool used is preferably 5% by mass to 50% by mass, more preferably 5% by mass, based on the total amount of polyols. % to 30% by mass.

胺基甲酸酯系黏著劑視需要亦可包含黏著性賦予劑。黏著性賦予劑只要可對胺基甲酸酯系黏著劑賦予黏著性或可提高黏著性,則並無特別限定。作為黏著性賦予劑,例如可列舉作為丙烯酸系黏著劑中可包含的黏著性賦予樹脂而所述者。The urethane-based adhesive may also contain an adhesiveness imparting agent as needed. The tackiness imparting agent will not be specifically limited as long as it can impart tackiness to a urethane type adhesive, or can improve tackiness. As an tackiness imparting agent, what was mentioned as the tackiness provision resin which can be contained in an acryl-type adhesive is mentioned, for example.

於胺基甲酸酯系黏著劑包含黏著性賦予劑的情況下,就硬化後的物性與性能的平衡的觀點而言,黏著性賦予劑的含量較佳為黏著劑組成物總量的10質量%~60質量%,更佳為10質量%~50質量%。When the urethane-based adhesive contains an adhesive agent, the content of the adhesive agent is preferably 10% by mass of the total amount of the adhesive composition from the viewpoint of a balance between physical properties and performance after hardening. % to 60% by mass, more preferably 10% to 50% by mass.

胺基甲酸酯系黏著劑視需要亦可包含反應性單官能化合物。藉由包含反應性單官能化合物,成為黏著劑的硬化後的黏著力(黏著強度)更優異者。The urethane-based adhesive may also contain a reactive monofunctional compound as needed. By including a reactive monofunctional compound, the adhesive becomes more excellent in the adhesive force (adhesive strength) after hardening.

反應性單官能化合物只要為於胺基甲酸酯反應中具有反應性,且可提高黏著劑的硬化後的黏著力(黏著強度)的單官能化合物,則並無特別限定。具體而言,可列舉:作為可用於末端NCO預聚物的合成的單醇而所述的單醇、單官能異氰酸酯化合物(單醇與二異氰酸酯的反應物等)、其他的能夠進行胺基甲酸酯反應的單官能組成物(胺、醯胺、硫醇、羧酸等)等。所使用的反應性單官能化合物可為單獨一種,亦可為兩種以上。就安全性及通用性的觀點而言,較佳為單官能異氰酸酯化合物,更佳為單醇與二異氰酸酯的反應物。作為單醇與二異氰酸酯的反應物,可列舉拜耳(Bayer)公司的商品名「添加劑(additive)TI」等。The reactive monofunctional compound is not particularly limited as long as it is a monofunctional compound that is reactive in the urethane reaction and can increase the adhesive force (adhesive strength) of the adhesive after hardening. Specifically, examples include the monoalcohols described above as monoalcohols that can be used in the synthesis of terminal NCO prepolymers, monofunctional isocyanate compounds (reaction products of monoalcohols and diisocyanates, etc.), and other compounds capable of performing aminoformation. Monofunctional composition of ester reaction (amine, amide, thiol, carboxylic acid, etc.), etc. The reactive monofunctional compound used may be single type, or may be two or more types. From the viewpoints of safety and versatility, monofunctional isocyanate compounds are preferred, and reactants of monoalcohols and diisocyanates are more preferred. As a reaction product of a monoalcohol and a diisocyanate, Bayer (Bayer) company brand name "additive (additive) TI" etc. are mentioned.

於胺基甲酸酯系黏著劑包含反應性單官能化合物的情況下,就硬化後的性能的觀點而言,反應性單官能化合物的使用量較佳為黏著劑總量的5質量%~50質量%,更佳為5質量%~30質量%。When the urethane-based adhesive contains a reactive monofunctional compound, the amount of the reactive monofunctional compound used is preferably 5% by mass to 50% by mass of the total amount of the adhesive from the viewpoint of performance after curing. % by mass, more preferably 5% by mass to 30% by mass.

胺基甲酸酯系黏著劑視需要亦可包含添加劑。作為添加劑,可列舉:胺基甲酸酯觸媒、塑化劑(丙烯酸酯系塑化劑、鄰苯二甲酸二酯類、環氧化六氫鄰苯二甲酸二酯類、伸烷基二羧酸二酯類、烷基苯類等)、填充劑(重質碳酸鈣、脂肪酸處理碳酸鈣、燻製二氧化矽、沈澱性二氧化矽、碳黑、滑石、氧化鈦、氣球體(balloon)、顆粒等)、抗氧化劑(受阻酚類等)、阻燃劑、觸變性賦予劑(膠質二氧化矽、有機膨潤土、脂肪酸醯胺、聚醯胺蠟、氫化蓖麻油等)、紫外線吸收劑(苯并三唑類、受阻胺類等)、防老化劑(受阻酚類、硫醇類、硫醚類、二硫代羧酸鹽類、硫脲類、硫代磷酸鹽類、硫醛類等)、密接劑(環氧化合物、矽烷偶合劑等)、脫水劑等。The urethane-based adhesive may contain additives as necessary. Examples of additives include: urethane catalysts, plasticizers (acrylate plasticizers, phthalic acid diesters, epoxidized hexahydrophthalic acid diesters, alkylene dicarboxylates, etc.) acid diesters, alkylbenzenes, etc.), fillers (ground calcium carbonate, fatty acid treated calcium carbonate, fumed silica, precipitated silica, carbon black, talc, titanium oxide, balloon, particles, etc.), antioxidants (hindered phenols, etc.), flame retardants, thixotropy imparting agents (colloidal silica, organic bentonite, fatty acid amides, polyamide waxes, hydrogenated castor oil, etc.), ultraviolet absorbers (benzene triazoles, hindered amines, etc.), anti-aging agents (hindered phenols, mercaptans, thioethers, dithiocarboxylates, thioureas, thiophosphates, thioaldehydes, etc.) , bonding agent (epoxy compound, silane coupling agent, etc.), dehydrating agent, etc.

作為胺基甲酸酯觸媒,可列舉:DBU系觸媒、胺系觸媒、有機羧酸金屬鹽、咪唑系觸媒等。作為DBU系觸媒,可列舉:DBU[1,8-二氮雜雙環[5.4.0]十一烯-7]、DBU苯酚鹽、DBU辛酸鹽、DBU甲酸鹽等。作為胺系觸媒,可列舉:單胺(三乙基胺等)、二胺(N,N,N',N'-四甲基乙二胺等)、三胺(四甲基胍等)、環狀胺(三乙二胺等)、醇胺(二甲基胺基甲醇等)、醚胺(雙(2-二甲基胺基乙基)醚等)等。作為有機羧酸金屬鹽,可列舉:Sn系(二丁基錫二月桂酸酯、辛酸錫等)、Pb系(辛酸鉛等)、Zn系(辛酸鋅等)等。作為咪唑系觸媒,可列舉:2-甲基咪唑、1,2-二甲基咪唑等。Examples of the urethane catalyst include DBU-based catalysts, amine-based catalysts, organic carboxylic acid metal salts, imidazole-based catalysts, and the like. Examples of the DBU-based catalyst include DBU[1,8-diazabicyclo[5.4.0]undecene-7], DBU phenate, DBU octanoate, DBU formate, and the like. Examples of amine-based catalysts include monoamines (triethylamine, etc.), diamines (N,N,N',N'-tetramethylethylenediamine, etc.), triamines (tetramethylguanidine, etc.) , cyclic amines (triethylenediamine, etc.), alcohol amines (dimethylaminomethanol, etc.), ether amines (bis(2-dimethylaminoethyl) ether, etc.), etc. Examples of metal organic carboxylic acid salts include Sn-based (dibutyltin dilaurate, tin octoate, etc.), Pb-based (lead octoate, etc.), Zn-based (zinc octoate, etc.), and the like. As an imidazole type catalyst, 2-methylimidazole, 1, 2- dimethylimidazole, etc. are mentioned.

胺基甲酸酯系黏著劑的製作方法並無特別限制。例如,可藉由將胺基甲酸酯系黏著劑中所含的聚合物成分、與視需要包含的其他成分混合而製作為一液型的胺基甲酸酯系黏著劑。胺基甲酸酯系黏著劑亦可為實質上不包含溶媒的無溶媒型黏著劑。若胺基甲酸酯系黏著劑實質上不包含溶媒,則於藉由熱使黏著劑硬化時,可抑制由臭氣、揮發性有機化合物(VOC)等的發生而引起的環境污染。The method for preparing the urethane-based adhesive is not particularly limited. For example, a one-pack type urethane adhesive can be produced by mixing the polymer component contained in the urethane adhesive and other components as needed. The urethane-based adhesive may be a solvent-free adhesive that does not substantially contain a solvent. If the urethane-based adhesive does not substantially contain a solvent, when the adhesive is hardened by heat, environmental pollution due to generation of odor, volatile organic compounds (VOC), and the like can be suppressed.

(填料) 黏著層亦可包含填料。藉由黏著層包含填料,可獲得使黏著層的外表面(與基材側相反的面)粗糙化等效果。 填料的材質並無特別限制,可為樹脂等有機物質,亦可為金屬、金屬氧化物等無機物質,抑或可為有機物質與無機物質的組合。另外,黏著層中所含的填料可為單獨一種,亦可為兩種以上。(Filler) The adhesive layer may contain a filler. By containing the filler in the adhesive layer, effects such as roughening the outer surface (the surface opposite to the substrate side) of the adhesive layer can be obtained. The material of the filler is not particularly limited, and may be organic substances such as resins, inorganic substances such as metals and metal oxides, or a combination of organic substances and inorganic substances. In addition, the filler contained in the adhesive layer may be a single type or two or more types.

填料的體積平均粒子徑並無特別限制。例如可選自1 μm~20 μm的範圍中。本說明書中填料的體積平均粒子徑為藉由雷射繞射法所測定的體積基準的粒度分佈中自小徑側的累計成為50%時的粒子徑(D50)。The volume average particle diameter of the filler is not particularly limited. For example, it can be selected from the range of 1 μm to 20 μm. The volume average particle diameter of the filler in this specification is the particle diameter (D50) when the accumulation from the small diameter side becomes 50% in the volume-based particle size distribution measured by the laser diffraction method.

就與黏著層中所含的黏著劑的親和性的觀點而言,填料較佳為樹脂粒子。作為構成樹脂粒子的樹脂,可列舉:丙烯酸樹脂、烯烴樹脂、苯乙烯樹脂、丙烯腈樹脂、矽酮樹脂等。就抑制對成形後的封裝的殘渣的觀點而言,較佳為丙烯酸樹脂。From the viewpoint of affinity with the adhesive contained in the adhesive layer, the filler is preferably resin particles. Examples of the resin constituting the resin particles include acrylic resins, olefin resins, styrene resins, acrylonitrile resins, silicone resins, and the like. From the viewpoint of suppressing residues on the molded package, an acrylic resin is preferable.

<基材> 基材的材質並無特別限制。就對模具的追隨性的觀點而言,較佳為樹脂。作為樹脂,可列舉:聚對苯二甲酸乙二酯(Polyethylene terephthalate,PET)等聚酯、聚醯亞胺、聚醯胺、聚酯醚、聚醯胺醯亞胺、含氟樹脂等。於使用樹脂的情況下,較佳為對密封步驟中的加熱溫度具有充分的耐熱性者。<Base Material> The material of the base material is not particularly limited. From the viewpoint of mold followability, resin is preferable. Examples of the resin include polyesters such as polyethylene terephthalate (PET), polyimides, polyamides, polyester ethers, polyamideimides, and fluorine-containing resins. When using resin, it is preferable that it has sufficient heat resistance with respect to the heating temperature in a sealing process.

視需要亦可對基材的設置有黏著層之側的面實施用以提高基材與黏著層之間的密接力的處理。作為處理的方法,可列舉:電暈處理、電漿處理等表面處理,底塗劑(底漆)的塗佈等。If necessary, treatment for improving the adhesion between the base material and the adhesive layer may be performed on the surface of the base material on which the adhesive layer is provided. As the method of treatment, surface treatment such as corona treatment and plasma treatment, application of primer (primer), and the like can be mentioned.

視需要亦可對基材的背面(與黏著層側相反的面)賦予用以調節黏著膜的自卷的捲出性的背面處理劑。作為背面處理劑,可列舉:矽酮樹脂、含氟樹脂、聚乙烯醇、具有烷基的樹脂等單體、改質體、混合物等。If necessary, a back surface treatment agent for adjusting the self-rolling unwinding property of the adhesive film may be provided to the back surface of the substrate (the surface opposite to the adhesive layer side). Examples of the back surface treatment agent include monomers such as silicone resins, fluorine-containing resins, polyvinyl alcohol, and resins having an alkyl group, modified products, and mixtures.

視需要為了抑制於黏著膜的捲出時、自黏附體的剝離時等的靜電的發生,亦可對基材的背面或設置有黏著層之側的面賦予抗靜電劑。作為抗靜電劑,可列舉:四級銨鹽、吡啶鎓鹽、具有一級胺基~三級胺基等陽離子性基的陽離子性抗靜電劑、具有磺酸鹽基、硫酸酯鹽基、磷酸酯鹽基等陰離子性基的陰離子系抗靜電劑、胺基酸系、胺基酸硫酸酯系等兩性抗靜電劑、胺基醇系、甘油系、聚乙二醇系等具有非離子性基的非離子系抗靜電劑、對該些抗靜電劑進行高分子量化的高分子型抗靜電劑等。該些抗靜電劑就透明性良好的方面而言亦較佳。 [實施例]If necessary, an antistatic agent may be added to the back surface of the base material or the surface on which the adhesive layer is provided in order to suppress the generation of static electricity when the adhesive film is unwound or peeled from the adherend. Examples of antistatic agents include: quaternary ammonium salts, pyridinium salts, cationic antistatic agents having cationic groups such as primary to tertiary amino groups, sulfonate groups, sulfate ester groups, phosphate ester groups, etc. Anionic antistatic agents with anionic bases such as salt bases, amphoteric antistatic agents such as amino acid series and amino acid sulfate series, amino alcohol series, glycerin series, polyethylene glycol series and other nonionic antistatic agents Nonionic antistatic agents, polymer antistatic agents obtained by increasing the molecular weight of these antistatic agents, and the like. These antistatic agents are also preferable in terms of good transparency. [Example]

以下,基於實施例而對本實施形態的脫模膜進行說明。但是,本實施形態並不限定於以下的實施例。Hereinafter, the release film of this embodiment is demonstrated based on an Example. However, this embodiment is not limited to the following examples.

<實施例1> 調配黏著劑A 100質量份、觸媒0.5質量份、以及溶劑(甲苯與甲基異丁基酮的混合物,質量比為1:1)275質量份,藉由分散器進行攪拌而製備黏著層形成用組成物。以黏著層的厚度成為3 μm的方式將該黏著層形成用組成物塗佈於基材(厚度為50 μm的PET膜)的其中一面的整個面上,於120℃下加熱1分鐘而形成黏著層,從而製作支撐體。繼而,如圖2所示般利用層壓法將長度為232 mm、寬度為67 mm、厚度為9 μm的銅箔(「F2-WS」,古河電氣工業股份有限公司)貼合於支撐體的黏著層,形成電磁波遮蔽片,並衝壓成特定的形狀而製作脫模膜。<Example 1> Prepare 100 parts by mass of adhesive A, 0.5 parts by mass of catalyst, and 275 parts by mass of solvent (mixture of toluene and methyl isobutyl ketone, mass ratio: 1:1), and stir with a disperser And the composition for adhesive layer formation was prepared. The composition for forming an adhesive layer was applied on the entire surface of one of the substrates (PET film with a thickness of 50 μm) so that the thickness of the adhesive layer became 3 μm, and heated at 120° C. for 1 minute to form an adhesive layer. layer to make a support. Next, as shown in Fig. 2, a copper foil with a length of 232 mm, a width of 67 mm, and a thickness of 9 μm ("F2-WS", Furukawa Electric Co., Ltd.) was bonded to the surface of the support. The adhesive layer forms an electromagnetic wave shielding sheet and is stamped into a specific shape to make a release film.

<實施例2> 調配黏著劑B 100質量份、交聯劑A 10質量份、以及溶劑(甲苯與甲基乙基酮的混合物,質量比為8:2)227質量份,藉由分散器進行攪拌而製備黏著層形成用組成物。以黏著層的厚度成為3 μm的方式將該黏著層形成用組成物塗佈於基材(厚度為38 μm的PET膜)的其中一面的整個面上,於100℃下加熱1分鐘而形成黏著層,從而製作支撐體。繼而,利用離子鍍敷法以厚度成為1 μm的方式於黏著層的整個面形成鋁層,並形成電磁波遮蔽片,衝壓成特定的形狀而製作脫模膜。<Example 2> 100 parts by mass of adhesive B, 10 parts by mass of crosslinking agent A, and 227 parts by mass of solvent (mixture of toluene and methyl ethyl ketone, mass ratio: 8:2) were prepared by a disperser The composition for forming an adhesive layer was prepared by stirring. The composition for forming an adhesive layer was applied to the entire surface of one of the substrates (PET film with a thickness of 38 μm) so that the thickness of the adhesive layer became 3 μm, and heated at 100° C. for 1 minute to form an adhesive layer. layer to make a support. Next, an aluminum layer was formed on the entire surface of the adhesive layer by ion plating to have a thickness of 1 μm, and an electromagnetic wave shielding sheet was formed, which was punched into a specific shape to produce a release film.

<實施例3> 調配黏著劑C 100質量份、交聯劑B 17.4質量份、填料10質量份、以及溶劑(甲苯與甲基乙基酮的混合物,質量比為8:2)87質量份,藉由分散器進行攪拌而製備黏著層形成用組成物。除使用該黏著層形成用組成物以外,與實施例2同樣地製作脫模膜。<Example 3> Prepare 100 parts by mass of adhesive C, 17.4 parts by mass of crosslinking agent B, 10 parts by mass of filler, and 87 parts by mass of solvent (mixture of toluene and methyl ethyl ketone, mass ratio: 8:2), The composition for forming an adhesive layer was prepared by stirring with a disperser. Except having used this composition for adhesive layer formation, it carried out similarly to Example 2, and produced the release film.

<比較例1> 使用與實施例2同樣地製備的黏著層形成用組成物,與實施例2同樣地將黏著層形成於基材上而製作支撐體。繼而,與實施例1同樣地將電磁波遮蔽片形成於黏著層上而製作脫模膜。<Comparative example 1> Using the composition for adhesive layer formation prepared similarly to Example 2, it carried out similarly to Example 2, formed the adhesive layer on the base material, and produced the support body. Next, the electromagnetic wave shielding sheet was formed on the adhesive layer similarly to Example 1, and the release film was produced.

脫模膜的製作中使用的各材料的詳細情況如下所述。 (黏著劑) ・黏著劑A:加成反應型矽酮系黏著劑,商品名「LTC755」,固體成分為30質量%,東麗道康寧(Toray Dow Corning)股份有限公司 ・黏著劑B:丙烯酸系黏著劑,商品名「S-43」,固體成分為24質量%,綜研化學股份有限公司,包含丙烯酸丁酯(BA)與丙烯酸4-羥基丁酯(4HBA)的混合單體 ・黏著劑C:丙烯酸系黏著劑,商品名「FS-1208」,固體成分為45質量%,獅王精化(Lion Specialty Chemicals)股份有限公司,包含甲基丙烯酸酯的多種的混合單體 (觸媒) ・鉑觸媒(商品名「NC-25」,東麗道康寧(Toray Dow Corning)股份有限公司) (交聯劑) ・交聯劑A:商品名「克羅奈特(Coronate)HL」,固體成分為75質量%,東曹(Tosoh)股份有限公司,三羥甲基丙烷/六亞甲基二異氰酸酯三聚體加成物的75%乙酸乙酯溶液,一分子中的異氰酸酯基數:3個 ・交聯劑B:商品名「多耐德(Duranate)E405-80T」,固體成分為80質量%,旭化成化學股份有限公司,聚異氰酸酯系交聯劑(六亞甲基二異氰酸酯交聯劑(HMDI)),一分子中的異氰酸酯基數:2個 ・填料:交聯丙烯酸中分散粒子,商品名「MZ-10HN」,體積平均粒子徑為10 μm,綜研化學股份有限公司The details of each material used for preparation of the release film are as follows. (Adhesive) ・Adhesive A: Addition reaction type silicone adhesive, trade name "LTC755", solid content 30% by mass, Toray Dow Corning Co., Ltd. ・Adhesive B: Acrylic Adhesive, trade name "S-43", solid content 24% by mass, Soken Chemical Co., Ltd., mixed monomer/adhesive C containing butyl acrylate (BA) and 4-hydroxybutyl acrylate (4HBA): Acrylic adhesive, trade name "FS-1208", solid content 45% by mass, Lion Specialty Chemicals Co., Ltd., various mixed monomers containing methacrylate (catalyst) ・Platinum catalyst (Brand name "NC-25", Toray Dow Corning Co., Ltd.) (Crosslinking agent) ・Crosslinking agent A: Brand name "Coronate HL", solid content 75 mass %, Tosoh Co., Ltd., 75% ethyl acetate solution of trimethylolpropane/hexamethylene diisocyanate trimer adduct, number of isocyanate groups in one molecule: 3 ・Crosslinking agent B: Brand name "Duranate (Duranate) E405-80T", solid content 80% by mass, Asahi Kasei Chemical Co., Ltd., polyisocyanate-based crosslinking agent (hexamethylene diisocyanate crosslinking agent (HMDI)), Number of isocyanate groups per molecule: 2 ・Filler: Cross-linked acrylic medium-dispersed particles, trade name "MZ-10HN", volume average particle diameter 10 μm, Soken Chemical Co., Ltd.

<評價試驗> 使用所製作的脫模膜來進行以下的評價試驗。<Evaluation test> The following evaluation test was performed using the produced release film.

(1)黏著層-電磁波遮蔽片間剝離力 於藉由層壓法形成電磁波遮蔽片的實施例1及比較例1中,將所製作的脫模膜投入至170℃的環境下,經過特定的時間後,利用騰喜龍萬能材料試驗機(A&D股份有限公司製造)以剝離角度180°、剝離速度0.3 m/min的剝離條件而測定剝離力(N/50 mm)。將結果示於表1。 於藉由離子鍍敷法形成電磁波遮蔽片的實施例2及實施例3中,將所製作的脫模膜切割成特定的大小,以黏著層在上方的方式放置於170℃的加熱板上,並將特定量的密封材(商品名「CEL-9750」,日立化成股份有限公司)分散於黏著層上,載置厚度為100 μm的PET膜。繼而,於PET膜上載置4 kg的砝碼,放置3分鐘直至密封材硬化為止。然後,將脫模膜切割成50 mm寬度,並投入至170℃的環境下。經過1分鐘後,利用騰喜龍萬能材料試驗機(A&D股份有限公司製造)以剝離角度180°、剝離速度0.3 m/min的剝離條件而測定剝離力。將結果示於表1。(1) Peeling force between the adhesive layer and the electromagnetic wave shielding sheet In Example 1 and Comparative Example 1 where the electromagnetic wave shielding sheet was formed by a lamination method, the release film produced was placed in an environment of 170°C, and after a specific After a period of time, the peeling force (N/50 mm) was measured using a Tengsilon universal material testing machine (manufactured by A&D Co., Ltd.) under the peeling conditions of a peeling angle of 180° and a peeling speed of 0.3 m/min. The results are shown in Table 1. In Example 2 and Example 3 where the electromagnetic wave shielding sheet was formed by ion plating, the produced release film was cut into a specific size and placed on a heating plate at 170° C. with the adhesive layer on top. A specific amount of sealing material (trade name "CEL-9750", Hitachi Chemical Co., Ltd.) was dispersed on the adhesive layer, and a PET film with a thickness of 100 μm was placed. Next, a weight of 4 kg was placed on the PET film, and left for 3 minutes until the sealing material hardened. Then, the release film was cut into a width of 50 mm, and put into an environment of 170°C. After 1 minute, the peeling force was measured using a Tengsilon universal material testing machine (manufactured by A&D Co., Ltd.) under the peeling conditions of a peeling angle of 180° and a peeling speed of 0.3 m/min. The results are shown in Table 1.

(2)電磁波遮蔽片的轉印性 將實施例1及比較例1中製作的脫模膜切割成特定的大小,以黏著層在上方的方式放置於170℃的加熱板上,並將特定量的密封材(商品名「CEL-9750」,日立化成股份有限公司)分散於黏著層上,載置厚度為100 μm的PET膜。繼而,於PET膜上載置4 kg的砝碼,放置3分鐘直至密封材硬化為止。然後,自支撐體(基材及黏著層)剝離電磁波遮蔽片,以目視確認電磁波遮蔽片的轉印性。 於實施例2及實施例3中,於與黏著層-電磁波遮蔽片間剝離力的評價同樣地使密封材硬化的狀態下,自支撐體(基材及黏著層)剝離電磁波遮蔽片,以目視確認電磁波遮蔽片的轉印性。(2) Transferability of electromagnetic wave shielding sheet Cut the release films produced in Example 1 and Comparative Example 1 into specific sizes, place them on a heating plate at 170°C with the adhesive layer on top, and apply a specific amount of The sealing material (trade name "CEL-9750", Hitachi Chemical Co., Ltd.) was dispersed on the adhesive layer, and a PET film with a thickness of 100 μm was placed. Next, a weight of 4 kg was placed on the PET film, and left for 3 minutes until the sealing material hardened. Then, the electromagnetic wave shielding sheet was peeled off from the support (base material and adhesive layer), and the transferability of the electromagnetic wave shielding sheet was visually confirmed. In Examples 2 and 3, the electromagnetic wave shielding sheet was peeled off from the support (substrate and adhesive layer) in the same manner as the evaluation of the peeling force between the adhesive layer and the electromagnetic wave shielding sheet, and the electromagnetic wave shielding sheet was visually observed. The transferability of the electromagnetic shielding sheet was confirmed.

關於電磁波遮蔽片的轉印性,將可於電磁波遮蔽片不發生褶皺、彎曲、破損等地自支撐體剝離的情況評價為「可」,將於電磁波遮蔽片發生褶皺、彎曲、破損等或無法自支撐體剝離的情況評價為「不可」。將結果示於表1。Regarding the transferability of the electromagnetic wave shielding sheet, it was evaluated as "possible" when the electromagnetic wave shielding sheet could be peeled off from the support without wrinkles, bending, damage, etc., and when the electromagnetic wave shielding sheet was wrinkled, bent, damaged, etc. The case where peeling from the support was evaluated as "impossible". The results are shown in Table 1.

[表1]

Figure 106116563-A0304-0001
[Table 1]
Figure 106116563-A0304-0001

如表1的結果所示般,黏著層與電磁波遮蔽片之間的剝離力為0.10 N/50 mm~2.00 N/50 mm的實施例的脫模膜的電磁波遮蔽片的轉印性良好。另一方面,黏著層與電磁波遮蔽片之間的剝離力未滿0.10 N/50 mm的比較例的脫模膜中,於剝離的電磁波遮蔽片產生褶皺,電磁波遮蔽片的轉印性較實施例差。As shown in the results in Table 1, the release film of the example in which the peeling force between the adhesive layer and the electromagnetic wave shielding sheet was 0.10 N/50 mm to 2.00 N/50 mm had good transferability to the electromagnetic wave shielding sheet. On the other hand, in the release film of the comparative example in which the peeling force between the adhesive layer and the electromagnetic wave shielding sheet was less than 0.10 N/50 mm, wrinkles were generated on the peeled electromagnetic wave shielding sheet, and the transferability of the electromagnetic wave shielding sheet was lower than that of the examples. Difference.

將日本專利申請案第2016-091947號的揭示整體藉由參照而併入至本說明書中。將本說明書中所記載的所有文獻、專利申請案及技術規格與具體且各個地記載有藉由參照而併入各個文獻、專利申請案及技術規格的情況同等程度地,藉由參照而併入至本說明書中。The entire disclosure of Japanese Patent Application No. 2016-091947 is incorporated in this specification by reference. All documents, patent applications and technical specifications described in this specification are incorporated by reference to the same extent as if each document, patent application and technical specification were specifically and individually stated to be incorporated by reference. to this manual.

10‧‧‧脫模膜 20‧‧‧支撐體 30‧‧‧電磁波遮蔽片 40‧‧‧黏著層 50‧‧‧基材 10‧‧‧Release film 20‧‧‧Support 30‧‧‧Electromagnetic wave shielding sheet 40‧‧‧adhesive layer 50‧‧‧substrate

圖1為表示本實施形態的脫模膜的結構的一例的概略剖面圖。 FIG. 1 is a schematic cross-sectional view showing an example of the structure of a release film according to this embodiment.

圖2為表示本實施形態的脫模膜的結構的一例的概略平面圖。 Fig. 2 is a schematic plan view showing an example of the structure of the release film of the present embodiment.

10‧‧‧脫模膜 10‧‧‧Release film

20‧‧‧支撐體 20‧‧‧Support

30‧‧‧電磁波遮蔽片 30‧‧‧Electromagnetic wave shielding sheet

40‧‧‧黏著層 40‧‧‧adhesive layer

50‧‧‧基材 50‧‧‧substrate

Claims (3)

一種脫模膜,其包含:支撐體,含有基材及配置於所述基材上的黏著層;以及電磁波遮蔽片,配置於所述支撐體的所述黏著層上,且所述黏著層與所述電磁波遮蔽片之間的剝離力為0.10N/50mm~2.00N/50mm,其中所述電磁波遮蔽片的厚度為0.01μm~12μm,所述黏著層的厚度為1μm~3μm。 A release film, comprising: a support body, including a base material and an adhesive layer arranged on the base material; and an electromagnetic wave shielding sheet, arranged on the adhesive layer of the support body, and the adhesive layer and the adhesive layer The peeling force between the electromagnetic wave shielding sheets is 0.10N/50mm-2.00N/50mm, wherein the thickness of the electromagnetic wave shielding sheet is 0.01μm-12μm, and the thickness of the adhesive layer is 1μm-3μm. 如申請專利範圍第1項所述的脫模膜,其中所述黏著層包含選自由矽酮系黏著劑及丙烯酸系黏著劑所組成的群組中的至少一種。 The release film as described in claim 1 of the patent application, wherein the adhesive layer includes at least one selected from the group consisting of silicone adhesives and acrylic adhesives. 如申請專利範圍第1項或第2項所述的脫模膜,其用於半導體裝置的製造,所述半導體裝置的製造包括將所述電磁波遮蔽片轉印至對半導體元件進行密封的密封材的步驟。 The release film according to claim 1 or claim 2 of the patent application, which is used in the manufacture of a semiconductor device, the manufacture of which includes transferring the electromagnetic wave shielding sheet to a sealing material for sealing a semiconductor element A step of.
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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111699092B (en) * 2018-02-27 2023-03-28 三菱化学株式会社 Polyester film
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0817855A (en) * 1994-06-29 1996-01-19 Nitto Denko Corp Manufacture of semiconductor device and laminate used therefor

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08288686A (en) * 1995-04-20 1996-11-01 Nec Corp Semiconductor device
JP4133637B2 (en) 2003-07-11 2008-08-13 三井化学株式会社 Electromagnetic wave shielding sheet for semiconductor element adhesion and semiconductor device
JP2007287937A (en) 2006-04-17 2007-11-01 Kyocera Chemical Corp Resin-sealed semiconductor device and its manufacturing method
JP5120266B6 (en) * 2007-01-31 2018-06-27 富士通セミコンダクター株式会社 Semiconductor device and manufacturing method thereof
JP5563981B2 (en) * 2008-08-28 2014-07-30 三井化学東セロ株式会社 Mold release film for manufacturing semiconductor resin package, and method for manufacturing semiconductor resin package using the same
KR101388972B1 (en) * 2009-03-31 2014-04-25 주식회사 잉크테크 process for preparation of laminated metal film
JP2012122058A (en) * 2010-11-18 2012-06-28 Nitto Denko Corp Die bond film, dicing die bond film, method of manufacturing die bond film, and semiconductor device having die bond film
JP2013021270A (en) * 2011-07-14 2013-01-31 Nitto Denko Corp Film for manufacturing semiconductor device
KR101944200B1 (en) * 2012-06-08 2019-01-30 히타치가세이가부시끼가이샤 Method for manufacturing semiconductor device
JP5615471B1 (en) * 2013-03-22 2014-10-29 リンテック株式会社 Protective film forming film and protective film forming composite sheet
JP6184025B2 (en) * 2014-09-04 2017-08-23 信越ポリマー株式会社 Electromagnetic wave shielding film and method for producing flexible printed wiring board with electromagnetic wave shielding film

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0817855A (en) * 1994-06-29 1996-01-19 Nitto Denko Corp Manufacture of semiconductor device and laminate used therefor

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